Coating compositions having improved scratch resistance, coated substrates and methods related thereto

ABSTRACT

Coating compositions are provided which are formed from components comprising (a) at least one polysiloxane comprising at least one reactive functional group; (b) at least one reactant comprising at least one functional group that is reactive with at least one functional group selected from the at least one reactive functional group of the at least one polysiloxane and at least one functional group of at least one reactant; and (c) a plurality of particles, wherein each component is different, and wherein the at least one reactive functional group of the at least one polysiloxane and the at least one functional group of the at least one reactant are substantially nonreactive with the particles. A multi-component composite coating composition formed from a basecoat and a topcoat deposited from the curable coating composition also is provided. The multi-component composite coating compositions of the invention provide highly scratch resistant color-plus-clearcoatings capable of retaining scratch resistance after weathering.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a Continuation-in-Part application of U.S.patent application Ser. No. 09/489,132 filed Jan. 21, 2000, which is aContinuation-in-Part application of U.S. patent application Ser. No.09/365,069 filed Jul. 30, 1999. U.S. patent application Ser. No.09/489,132 claims the benefit of priority from Provisional PatentApplication Ser. No. 60/171,898 filed Dec. 23, 1999.

FIELD OF THE INVENTION

[0002] Certain embodiments of the present invention are directed tocompositions comprising at least one polysiloxane comprising at leastone reactive functional group, and a plurality of particles, wherein thereactive functional group of the at least one polysiloxane issubstantially nonreactive with the particles. Embodiments of the presentinvention also are directed to compositions comprising at least onepolysiloxane comprising at least one reactive functional group, at leastone reactant comprising at least one functional group that is reactivewith at least one functional group selected from the at least onereactive functional group of the at least one polysiloxane and at leastone functional group of at least one reactant, and a plurality ofparticles wherein the reactive functional group of the at least onepolysiloxane is substantially nonreactive with the particles. Otherembodiments of the present invention are directed to substrates coatedwith the aforementioned compositions. Further embodiments of the presentinvention are directed to methods for improving scratch resistance of asubstrate. It will be apparent to one of ordinary skill in the art thatspecific embodiments of the present invention may be directed to some orall of these aspects of the present invention as well as other desirableaspects.

BACKGROUND OF THE INVENTION

[0003] Color-plus-clearcoating systems involving the application of acolored or pigmented basecoat to a substrate followed by application ofa transparent or clearcoat over the basecoat have become increasinglypopular as original finishes for a number of consumer productsincluding, for example, automotive vehicles. The color-plus-clearcoatingsystems have outstanding appearance properties such as gloss anddistinctness of image, due in large part to the clearcoat. Suchcolor-plus-clearcoating systems have become popular for use withautomotive vehicles, aerospace applications, floor coverings such asceramic tiles and wood flooring, packaging coatings and the like.

[0004] Topcoat film-forming compositions, particularly those used toform the transparent clearcoat in color-plus-clearcoating systems forautomotive applications, are subject to defects that occur during theassembly process as well as damage from numerous environmental elements.Such defects during the assembly process include paint defects in theapplication or curing of the basecoat or the clearcoat. Damagingenvironmental elements include acidic precipitation, exposure toultraviolet radiation from sunlight, high relative humidity and hightemperatures, defects due to contact with objects causing scratching ofthe coated surface, and defects due to impact with small, hard objectsresulting in chipping of the coating surface.

[0005] Typically, a harder more highly crosslinked film may exhibitimproved scratch resistance, but it is less flexible and much moresusceptible to chipping or thermal cracking due to embrittlement of thefilm resulting from a high crosslink density. A softer, less crosslinkedfilm, while not prone to chipping or thermal cracking, is susceptible toscratching, waterspotting, and acid etch due to a low crosslink densityof the cured film.

[0006] Further, elastomeric automotive parts and accessories, forexample, elastomeric bumpers and hoods, are typically coated “off site”and shipped to automobile assembly plants. The coating compositionsapplied to such elastomeric substrates are typically formulated to bevery flexible so the coating can bend or flex with the substrate withoutcracking. To achieve the requisite flexibility, coating compositions foruse on elastomeric substrates often are formulated to produce coatingswith lower crosslink densities or to include flexibilizing adjuvantswhich act to lower the overall film glass transition temperature (Tg).While acceptable flexibility properties can be achieved with theseformulating techniques, they also can result in softer films that aresusceptible to scratching. Consequently, great expense and care must betaken to package the coated parts to prevent scratching of the coatedsurfaces during shipping to automobile assembly plants.

[0007] A number of patents teach the use of a coating comprising adispersion of colloidal silica in an alcohol-water solution of a partialcondensate of a silanol of the formula RSi(OH)₃ wherein at least 70weight percent of the partial condensate is the partial condensate ofCH₃Si(OH)₃. Representative, nonlimiting examples are U.S. Pat. Nos.3,986,997, 4,027,073, 4,239,738, 4,310,600 and 4,410,594.

[0008] U.S. Pat. No. 4,822,828 teaches the use of a vinyl functionalsilane in an aqueous, radiation curable, coating composition whichcomprises: (a) from 50 to 85 percent, based on the total weight of thedispersion, of a vinyl functional silane, (b) from 15 to 50 percent,based on the total weight of the dispersion of a multifunctionalacrylate, and (c) optionally, from 1 to 3 weight percent of aphotoinitiator. The vinyl-functional silane is the partial condensate ofsilica and a silane, such that at least sixty percent of the silane is avinyl-functional silane conforming to the formula(R)_(a)Si(R′)_(b)(R″)_(c) wherein R is allyl or vinyl functional alkyl;R′ is hydrolyzable alkoxy or methoxy; R″ is non-hydrolyzable, saturatedalkyl, phenyl, or siloxy, such that a+b+c=4; and a ≧1; b≧1; c≧0. Thepatent discloses that these coating compositions may be applied toplastic materials and cured by exposure to ultraviolet or electron beamirradiation to form a substantially clear, abrasion resistant layer.

[0009] U.S. Pat. No. 5,154,759 teaches a polish formulation comprising areactive amine functional silicone polymer and at least one otheringredient normally used in polish formulations. One such ingredientdisclosed in the patent is an abrasive, which is taught to be aluminumsilicate, diatomaceous earth, pumice, fuller's earth, bentonite, silica,tripoli, hydrated calcium silicate chalk, colloidal clay, magnesiumoxide red iron oxide, or tin oxide.

[0010] U.S. Pat. No. 5,686,012 describes modified particles comprisinginorganic colored or magnetic particles as core particles, and at leastone polysiloxane modified with at least one organic group which iscoated on the surfaces of the core particles. The patent also disclosesa water-based paint comprising a paint base material and the modifiedparticles as the pigment as well as a process for producing the modifiedparticles.

[0011] U.S. Pat. No. 5,853,809 discloses clearcoats in color-plus-clearsystems which have improved scratch resistance due to the inclusion inthe coating composition of inorganic particles such as colloidal silicaswhich have been surface modified with a reactive coupling agent viacovalent bonding.

[0012] Despite recent improvements in color-plus-clearcoating systems,there remains a need in the automotive coatings art for topcoats havinggood initial scratch resistance as well as enhanced post-weathering(“retained”) scratch resistance without embrittlement of the film due tohigh crosslink density. Moreover, it would be advantageous to providetopcoats for elastomeric substrates utilized in the automotive industrywhich are both flexible and resistant to scratching.

SUMMARY OF THE INVENTION

[0013] In one embodiment, the present invention is directed to acomposition formed from components comprising:

[0014] (a) at least one polysiloxane comprising at least one reactivefunctional group;

[0015] (b) at least one reactant comprising at least one functionalgroup that is reactive with at least one functional group selected fromthe at least one reactive functional group of the at least onepolysiloxane and at least one functional group of at least one reactant;and

[0016] (c) a plurality of particles selected from inorganic particles,composite particles, and mixtures thereof,

[0017] wherein each component is different, and

[0018] wherein the at least one reactive functional group of the atleast one polysiloxane and the at least one functional group of the atleast one reactant are substantially nonreactive with the particles.

[0019] In another embodiment, the present invention is directed to acomposition formed from components comprising:

[0020] (a) at least one polysiloxane comprising at least one reactivefunctional group;

[0021] (b) at least one reactant comprising at least one functionalgroup that is reactive with at least one functional group selected fromthe at least one reactive functional group of the at least onepolysiloxane and at least one functional group of at least one reactant;and

[0022] (c) a plurality of particles,

[0023] wherein each component is different,

[0024] wherein the at least one reactive functional group of the atleast one polysiloxane is substantially nonreactive with the pluralityof particles, and

[0025] wherein a retained scratch resistance of the composition whencured greater than the retained scratch resistance of a composition whencured that does not contain the plurality of particles.

[0026] In another embodiment, the present invention is directed to acomposition formed from components comprising:

[0027] (a) at least one polysiloxane comprising at least one reactivefunctional group;

[0028] (b) at least one reactant comprising at least one functionalgroup that is reactive with at least one functional group selected fromthe at least one reactive functional group of the at least onepolysiloxane and at least one functional group of at least one reactant;and

[0029] (c) a plurality of particles,

[0030] wherein each component is different,

[0031] wherein the at least one reactive functional group of the atleast one polysiloxane is substantially nonreactive with the particles,and

[0032] wherein a retained scratch resistance value of the compositionwhen cured is greater than a retained scratch resistance value of acomposition when cured that does not contain the plurality of particles.

[0033] In another embodiment, the present invention is directed to acomposition formed from components comprising:

[0034] (a) a polysiloxane comprising at least one reactive functionalgroup, the polysiloxane comprising at least one of the followingstructural units (I)

R¹ _(n)R² _(m)SiO₍₄₋ n-m)_(/2)  (I)

[0035] wherein each R¹, which may be identical or different, representsH, OH, or a monovalent hydrocarbon group; each R², which may beidentical or different, represents a group comprising at least onereactive functional group,

[0036] provided that when the polysiloxane is a partial condensate of asilanol, then less than 70% by weight of the partial condensate is thepartial condensate of CH₃Si(OH)₃; and

[0037] (b) a plurality of particles having an average particle size ofless than 100 nanometers prior to incorporation into the composition,

[0038] wherein each component is different, and

[0039] wherein the at least one reactive functional group of the atleast one polysiloxane is substantially nonreactive with the particles.

[0040] Additionally, a coated substrate is disclosed to be within thescope of the present invention which comprises a substrate and acomposition coated over at least a portion of the substrate, thecomposition being any of the foregoing compositions according to thepresent invention. The present invention also provides a method ofcoating a substrate which comprises applying any of the foregoingcompositions according to the present invention over at least a portionof the substrate. A coated metallic substrate also is provided whichcomprises a metallic substrate and a composition applied over at least aportion of the metallic substrate, the composition being any of theforegoing compositions according to the present invention. Coatedautomotive substrates also are disclosed to be within the presentinvention which comprise an automotive substrate which is coated, atleast in part, by any of the foregoing compositions according to thepresent invention. The present invention also provides methods of makingcoated automotive substrates comprising obtaining an automotivesubstrate and applying over at least a portion of the automotivesubstrate any of the foregoing compositions according to the presentinvention.

[0041] Also provided are multi-component composite coating compositionswhich comprise a basecoat deposited from a pigmented coatingcomposition, and any one of the foregoing coating compositions accordingto the present invention applied over at least a portion of the basecoatto form a topcoat. The present invention also provides methods formaking multi-component composite coating compositions comprising: (a)applying a pigmented composition to a substrate to form a basecoat; and(b) applying a topcoating composition over at least a portion of thebasecoat to form a topcoat thereon, the topcoating composition being anyof the foregoing compositions according to the present invention.

[0042] Methods of improving the scratch resistance of a polymericsubstrate or polymeric coating which comprise applying to the polymericsubstrate or polymeric coating any of the foregoing compositionsaccording to the present invention also are provided in anotherembodiment of the present invention. The present invention also providesmethods for retaining the gloss of a polymeric substrate or polymericcoating over a period of time which comprises applying to at least aportion of the polymeric substrate or polymeric coating any of theforegoing compositions according to the present invention. Also providedare methods for revitalizing the gloss of a polymeric substrate orpolymeric coating comprising applying to at least a portion of thepolymeric substrate or polymeric coating any of the foregoingcompositions according to the present invention.

[0043] Other than in the operating examples, or where otherwiseindicated, all numbers expressing quantities of ingredients, reactionconditions, and so forth used in the specification and claims are to beunderstood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that may vary depending upon the desired propertiessought to be obtained by the present invention. At the very least, andnot as an attempt to limit the application of the doctrine ofequivalents to the scope of the claims, each numerical parameter shouldat least be construed in light of the number of reported significantdigits and by applying ordinary rounding techniques.

[0044] Notwithstanding that the numerical ranges and parameters settingforth the broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

DETAILED DESCRIPTION OF THE DRAWINGS

[0045]FIG. 1 is a transmission electron micrograph (30,000×magnification) of a cross-section of a cured transparent topcoatingcomposition of the present invention which contains both colloidalsilica and polysiloxane;

[0046]FIG. 2 is a transmission electron micrograph (30,000×magnification) of a cross-section of a comparative example of atransparent topcoating composition which contains colloidal silica butnot polysiloxane;

[0047]FIG. 3 is a transmission electron micrograph of a cross-section ofthe cured transparent topcoating composition of FIG. 1, but viewed at54,000× magnification;

[0048]FIG. 4 is a transmission electron micrograph (105,000×magnification) of a cross-section of a cured transparent topcoatingcomposition of the present invention which included a preformeddispersion of colloidal silica and polysiloxane;

[0049]FIG. 5 is a graph of scratch depth as a function of load over agiven scratch distance showing scratch (mar) resistance of a commercialtwo-component polyurethane coating; and

[0050]FIG. 6 is a graph of scratch depth as a function of load over agiven scratch distance showing scratch (mar) resistance of atwo-component coating containing colloidal silica and polysiloxane ofthe present invention.

[0051]FIG. 7 is a transmission electron micrograph (105,000×magnification) of a cross-section of a cured transparent topcoatingcomposition of the present invention taken generally perpendicular tothe surface of the coating which included a preformed polysiloxanedispersion comprising 2% colloidal silica.

[0052]FIG. 8 is a transmission electron micrograph (105,000×magnification) of a cross-section of a cured transparent topcoatingcomposition of the present invention which included a preformedpolysiloxane dispersion comprising 2% colloidal silica taken at anglewith respect to the surface of the coating.

[0053]FIG. 9 is a transmission electron micrograph (105,000×magnification) of a cross-section of a cured transparent topcoatingcomposition of the present invention taken generally perpendicular tothe surface of the coating which included a preformed polysiloxanedispersion comprising 8.5% colloidal silica.

[0054]FIG. 10 is a transmission electron micrograph (105,000×magnification) of a cross-section of a cured transparent topcoatingcomposition of the present invention which included a preformedpolysiloxane dispersion comprising 8.5% colloidal silica taken at anglewith respect to the surface of the coating.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0055] In one embodiment, the present invention is directed to acomposition formed from components comprising:

[0056] (a) at least one polysiloxane comprising at least one reactivefunctional group;

[0057] (b) at least one reactant comprising at least one functionalgroup that is reactive with at least one functional group selected fromthe at least one reactive functional group of the at least onepolysiloxane and at least one functional group of at least one reactant;and

[0058] (c) a plurality of particles selected from inorganic particles,composite particles, and mixtures thereof,

[0059] wherein each component is different, and

[0060] wherein the at least one reactive functional group of the atleast one polysiloxane and the at least one functional group of the atleast one reactant are substantially nonreactive with the particles.

[0061] As used herein, “formed from” denotes open, e.g., “comprising,”claim language. As such, it is intended that a composition “formed from”a list of recited components be a composition comprising at least theserecited components, and can further comprise other nonrecited componentsduring the composition's formation.

[0062] Also, as used herein, the term “reactive” refers to a functionalgroup that forms a covalent bond with another functional group underconditions sufficient to cure the composition.

[0063] As used herein, the phrase “each component is different” refersto components which do not have the same chemical structure as othercomponents in the composition.

[0064] Furthermore, as used herein, by “substantially nonreactive” meansthat the functional groups of the at least one polysiloxane (a) and theat least one reactant, if present, do not tend to form covalent bondswith the particles.

[0065] In a further embodiment, the present invention is directed tocured compositions as previously described wherein at least one reactantis present during the formation of the coating composition. As usedherein, the “at least one reactant” refers to any material comprising afunctional group that is reactive with at least one functional groupselected from at least one functional group of the at least onepolysiloxane and at least one functional group of the material.

[0066] In another embodiment, the present invention is directed to acomposition formed from components comprising:

[0067] (a) at least one polysiloxane comprising at least one reactivefunctional group;

[0068] (b) at least one reactant comprising at least one functionalgroup that is reactive with at least one functional group selected fromthe at least one reactive functional group of the at least onepolysiloxane and at least one functional group of at least one reactant;and

[0069] (c) a plurality of particles,

[0070] wherein each component is different,

[0071] wherein the at least one reactive functional group of the atleast one polysiloxane is substantially nonreactive with the pluralityof particles, and

[0072] wherein a retained scratch resistance value of the compositionwhen cured is greater than the retained scratch resistance value of acomposition when cured that does not contain the plurality of particles.

[0073] The term “retained scratch resistance” referred to throughout thespecification and the appended claims will be described in detail below.

[0074] As used herein, the term “cure” as used in connection with acomposition, e.g., “a cured composition,” shall mean that anycrosslinkable components of the composition are at least partiallycrosslinked. In certain embodiments of the present invention, thecrosslink density of the crosslinkable components, i.e., the degree ofcrosslinking, ranges from 5% to 100% of complete crosslinking. In otherembodiments, the crosslink density ranges from 35% to 85% of fullcrosslinking. In other embodiments, the crosslink density ranges from50% to 85% of full crosslinking. One skilled in the art will understandthat the presence and degree of crosslinking, i.e., the crosslinkdensity, can be determined by a variety of methods, such as dynamicmechanical thermal analysis (DMTA) using a TA Instruments DMA 2980 DMTAanalyzer conducted under nitrogen. This method determines the glasstransition temperature and crosslink density of free films of coatingsor polymers. These physical properties of a cured material are relatedto the structure of the crosslinked network.

[0075] In another embodiment, the present invention is directed to acomposition formed from components comprising:

[0076] (a) at least one polysiloxane comprising at least one reactivefunctional group selected from a hydroxyl group, a carboxyl group, anisocyanate group, a blocked polyisocyanate group, a primary amine group,a secondary amine group, an amide group, a carbamate group, a ureagroup, a urethane group, a vinyl group, an unsaturated ester group suchas an acrylate group and a methacrylate group, a maleimide group, afumarate group, an onium salt group such as a sulfonium group and anammonium group, an anhydride group, a hydroxy alkylamide group, and anepoxy group; wherein m and n fulfill the requirements of 0<n<4, 0<m<4and 2≦(m+n)<4; and provided that when the at least one polysiloxane is apartial condensate of a silanol, then less than 70% by weight of thepartial condensate is the partial condensate of CH₃Si(OH)₃; and

[0077] (b) a plurality of particles having an average particle size ofless than 100 nanometers prior to incorporation into the composition,

[0078] wherein the at least one reactive functional group of the atleast one polysiloxane is substantially nonreactive with the particles.

[0079] In another embodiment, the present invention is directed to acomposition as previously described wherein the at least onepolysiloxane comprising at least one reactive functional group has atleast one of the following structural units (I)

R¹ _(n)R² _(m)SiO₍₄₋ n-m)/2  (I)

[0080] wherein each R¹, which may be identical or different, representsH, OH, or a monovalent hydrocarbon group; each R², which may beidentical or different, represents a group comprising at least onereactive functional group; wherein m and n fulfill the requirements of0<n<4, 0<m<4 and 2≦(m+n)<4.

[0081] As used herein, a “monovalent hydrocarbon group” means amonovalent group comprising a backbone repeat unit based exclusively oncarbon. As used herein, “monovalent” refers to a substituent group that,as a substituent group, forms only one single, covalent bond. Forexample, a monovalent group on the at least one polysiloxane will formone single covalent bond to a silicon atom in the backbone of the atleast one polysiloxane polymer. As used herein, “hydrocarbon groups” areintended to encompass both branched and unbranched hydrocarbon groups.

[0082] Thus, when referring to a “monovalent hydrocarbon group,” thehydrocarbon group can be branched or unbranched, acyclic or cyclic,saturated or unsaturated, or aromatic, and can contain from 1 to 24 (orin the case of an aromatic group from 3 to 24) carbon atoms. Nonlimitingexamples of such hydrocarbon groups include alkyl, alkoxy, aryl,alkaryl, and alkoxyaryl groups. Nonlimiting examples of lower alkylgroups include, for example, methyl, ethyl, propyl, and butyl groups. Asused herein, “lower alkyl” refers to alkyl groups having from 1 to 6carbon atoms. One or more of the hydrogen atoms of the hydrocarbon canbe substituted with heteroatoms. As used herein, heteroatoms” meanselements other than carbon, for example, oxygen, nitrogen, and halogenatoms.

[0083] As used herein, “siloxane” means a group comprising a backbonecomprising two or more —SiO— groups. For example, the siloxane groupsrepresented by R¹, which is discussed above, and R, which is discussedbelow, can be branched or unbranched, and linear or cyclic. The siloxanegroups can be substituted with pendant organic substituent groups, forexample, alkyl, aryl, and alkaryl groups. The organic substituent groupscan be substituted with heteroatoms, for example, oxygen, nitrogen, andhalogen atoms, reactive functional groups, for example, those reactivefunctional groups discussed above with reference to R², and mixtures ofany of the foregoing.

[0084] It should be understood that the “at least one polysiloxanecomprising at least one structural unit (I)” above is a polymer thatcontains at least two Si atoms per molecule. As used herein, the term“polymer” in meant to encompass oligomer, and includes withoutlimitation both homopolymers and copolymers. It should also beunderstood that the at least one polysiloxane can include linear,branched, dendritic or cyclic polysiloxanes.

[0085] Each of m and n depicted in the at least one structural unit (I)above fulfill the requirements of 0<n<4, 0<m<4 and 2≦(m+n)<4. When (m+n)is 3, the value represented by n can be 2 and the value represented by mis 1. Likewise, when (m+n) is 2, the value represented by each of n andm is 1.

[0086] In another embodiment, the present invention is directed to acomposition as described above, wherein R², which may be identical ordifferent, represents a group comprising at least one reactivefunctional group selected from a hydroxyl group, a carboxyl group, anisocyanate group, a blocked polyisocyanate group, a primary amine group,a secondary amine group, an amide group, a carbamate group, a ureagroup, a urethane group, a vinyl group, an unsaturated ester group suchas an acrylate group and a methacrylate group, a maleimide group, afumarate group, an onium salt group such as a sulfonium group and anammonium group, an anhydride group, a hydroxy alkylamide group, and anepoxy group.

[0087] In one embodiment, the present invention is directed to a curedcomposition as previously described in which the at least onepolysiloxane comprises reactive functional groups which are thermallycurable functional groups. In an alternative embodiment, at least one ofthe reactive functional groups of the polysiloxane can be curable byionizing radiation or actinic radiation. In another alternativeembodiment, the polysiloxane can comprise at least one functional groupwhich is curable by thermal energy and at least one functional groupwhich is curable by ionizing or actinic radiation.

[0088] As used herein, “ionizing radiation” means high energy radiationand/or the secondary energies resulting from conversion of this electronor other particle energy to neutron or gamma radiation, said energiesbeing at least 30,000 electron volts and can range from 50,000 to300,000 electron volts. While various types of ionizing irradiation aresuitable for this purpose, such as X-ray, gamma and beta rays, theradiation produced by accelerated high energy electrons or electron beamdevices is preferred. The amount of ionizing radiation in rads forcuring compositions according to the present invention can vary basedupon such factors as the components of the coating formulation, thethickness of the coating upon the substrate, the temperature of thecoating composition and the like. Generally, a 1 mil (25 micrometer)thick wet film of a coating composition according to the presentinvention can be cured in the presence of oxygen through its thicknessto a tack-free state upon exposure to from 0.5 to 5 megarads of ionizingradiation.

[0089] “Actinic radiation” is light with wavelengths of electromagneticradiation ranging from the ultraviolet (“UV”) light range, through thevisible light range, and into the infrared range. Actinic radiationwhich can be used to cure coating compositions of the present inventiongenerally has wavelengths of electromagnetic radiation ranging from 150to 2,000 nanometers (nm), from 180 to 1,000 nm, or from 200 to 500 nm.In one embodiment, ultraviolet radiation having a wavelength rangingfrom 10 to 390 nm can be used. Examples of suitable ultraviolet lightsources include mercury arcs, carbon arcs, low, medium or high pressuremercury lamps, swirl-flow plasma arcs and ultraviolet light emittingdiodes. Suitable ultraviolet light-emitting lamps are medium pressuremercury vapor lamps having outputs ranging from 200 to 600 watts perinch (79 to 237 watts per centimeter) across the length of the lamptube. Generally, a 1 mil (25 micrometer) thick wet film of a coatingcomposition according to the present invention can be cured through itsthickness to a tack-free state upon exposure to actinic radiation bypassing the film at a rate of 20 to 1000 feet per minute (6 to 300meters per minute) under four medium pressure mercury vapor lamps ofexposure at 200 to 1000 millijoules per square centimeter of the wetfilm.

[0090] Useful radiation-curable groups which can be present as reactivefunctional groups on the polysiloxane include unsaturated groups such asvinyl groups, vinyl ether groups, epoxy groups, maleimide groups,fumarate groups and combinations of the foregoing. In one embodiment,the UV curable groups can include acrylate groups, maleimides,fumarates, and vinyl ethers. Suitable vinyl groups include those havingunsaturated ester groups and vinyl ether groups as discussed below.

[0091] In another embodiment, the present invention is directed to acomposition as previously described, wherein the at least one reactantis selected from at least one curing agent.

[0092] In one embodiment, the present invention is directed to acomposition as previously described, wherein the at least onepolysiloxane comprises at least two reactive functional groups. The atleast one polysiloxane can have a reactive group equivalent weightranging from 50 to 1000 mg per gram of the at least one polysiloxane. Inone embodiment, the at least one polysiloxane has a hydroxyl groupequivalent weight ranging from 50 to 1000 mg KOH per gram of the atleast one polysiloxane. In another embodiment, the at least onepolysiloxane has a hydroxyl group equivalent weight ranging from 100 to300 mg KOH per gram of the at least one polysiloxane, while in anotherembodiment, the hydroxyl group equivalent weight ranges from 100 to 500mg KOH per gram.

[0093] In another embodiment, the present invention is directed to acomposition as previously described, wherein at least one R² grouprepresents a group comprising at least one reactive functional groupselected from a hydroxyl group and a carbamate group. In yet anotherembodiment, the present invention is directed to a composition aspreviously described, wherein at least one R² group represents a groupcomprising at least two reactive functional groups selected from ahydroxyl group and a carbamate group. In another embodiment, the presentinvention is directed to a composition as previously described, whereinat least one R² group represents a group comprising an oxyalkylene groupand at least two hydroxyl groups.

[0094] In one embodiment, the present invention is directed to acomposition as previously described, wherein the at least onepolysiloxane (a) has the following structure (II) or (III):

[0095] wherein: m has a value of at least 1; m′ ranges from 0 to 75; nranges from 0 to 75; n′ ranges from 0 to 75; each R, which may beidentical or different, is selected from H, OH, a monovalent hydrocarbongroup, and mixtures of any of the foregoing; and —R^(a) comprises thefollowing structure (IV):

—R³—X  (IV)

[0096] wherein —R³ is selected from an alkylene group, an oxyalkylenegroup, an alkylene aryl group, an alkenylene group, an oxyalkenylenegroup, and an alkenylene aryl group; and X represents a group whichcomprises at least one reactive functional group selected from ahydroxyl group, a carboxyl group, an isocyanate group, a blockedpolyisocyanate group, a primary amine group, a secondary amine group, anamide group, a carbamate group, a urea group, a urethane group, a vinylgroup, an unsaturated ester group such as an acrylate group and amethacrylate group, a maleimide group, a fumarate group, an onium saltgroup such as a sulfonium group and an ammonium group, an anhydridegroup, a hydroxy alkylamide group, and an epoxy group.

[0097] As used herein, “alkylene” refers to an acyclic or cyclic,saturated hydrocarbon group having a carbon chain length of from C₂ toC₂₅. Nonlimiting examples of suitable alkylene groups include, but arenot limited to, those derived from propenyl, 1-butenyl, 1-pentenyl,1-decenyl, and 1-heneicosenyl, such as, for example (CH₂)₃, (CH₂)₄,(CH₂)₅, (CH₂)₁₀, and (CH₂)₂₃, respectively, as well as isoprene andmyrcene.

[0098] As used herein, “oxyalkylene” refers to an alkylene groupcontaining at least one oxygen atom bonded to, and interposed between,two carbon atoms and having an alkylene carbon chain length of from C₂to C₂₅. Nonlimiting examples of suitable oxyalkylene groups includethose derived from trimethylolpropane monoallyl ether,trimethylolpropane diallyl ether, pentaerythritol monoallyl ether,polyethoxylated allyl alcohol, and polypropoxylated allyl alcohol, suchas —(CH₂)₃OCH₂C(CH₂OH)₂(CH₂CH₂—).

[0099] As used herein, “alkylene aryl” refers to an acyclic alkylenegroup substituted with at least one aryl group, for example, phenyl, andhaving an alkylene carbon chain length of C₂ to C₂₅. The aryl group canbe further substituted, if desired. Nonlimiting examples of suitablesubstituent groups for the aryl group include, but are not limited to,hydroxyl groups, benzyl groups, carboxylic acid groups, and aliphatichydrocarbon groups. Nonlimiting examples of suitable alkylene arylgroups include, but are not limited to, those derived from styrene and3-isopropenyl-∝,∝-dimethylbenzyl isocyanate, such as —(CH₂)₂C₆H₄— and—CH₂CH(CH₃)C₆H₃(C(CH₃)₂(NCO). As used herein, “alkenylene” refers to anacyclic or cyclic hydrocarbon group having one or more double bonds andhaving an alkenylene carbon chain length of C₂ to C₂₅. Nonlimitingexamples of suitable alkenylene groups include those derived frompropargyl alcohol and acetylenic diols, for example,2,4,7,9-tetramethyl-5-decyne-4,7-diol which is commercially availablefrom Air Products and Chemicals, Inc. of Allentown, Pa. as SURFYNOL 104.

[0100] Formulae (II) and (III) are diagrammatic, and are not intended toimply that the parenthetical portions are necessarily blocks, althoughblocks may be used where desired. In some cases the polysiloxane maycomprise a variety of siloxane units. This is increasingly true as thenumber of siloxane units employed increases, and especially true whenmixtures of a number of different siloxane units are used. In thoseinstances where a plurality of siloxane units are used and it is desiredto form blocks, oligomers can be formed which can be joined to form theblock compound. By judicious choice of reactants, compounds having analternating structure or blocks of alternating structure may be used.

[0101] In yet another embodiment, the present invention is directed toany composition as previously described, wherein the particles aredifferent from the at least one polysiloxane. In yet another embodiment,the present invention is directed to any composition as previouslydescribed, wherein the particles have an average particle size less than100 nanometers prior to incorporation into the composition. Methodsknown to one of ordinary skill in the art for measuring the averageparticle size are discussed in detail below.

[0102] In one embodiment, the present invention is directed to acomposition as previously described wherein the substituent group R³represents an oxyalkylene group. In another embodiment, R³ represents anoxyalkylene group, and X represents a group which comprises at least tworeactive functional groups.

[0103] In another embodiment, the present invention is directed to anycomposition as previously described comprising at least one polysiloxanehaving the structure (II) or (III) described above, wherein (n+m) rangesfrom 2 to 9. In yet another embodiment, in compositions comprising atleast one polysiloxane having the structure (II) or (III) describedabove, (n+m) ranges from 2 to 3. In another embodiment, in compositionscomprising at least one polysiloxane having the structure (II) or (III)described above, (n′+m′) ranges from 2 to 9. In another embodiment, incompositions comprising at least one polysiloxane having the structure(II) or (III) described above, (n′+m′) ranges from 2 to 3.

[0104] In one embodiment, the present invention is directed to anycomposition as previously described wherein X represents a groupcomprising at least one reactive functional group selected from ahydroxyl group and a carbamate group. In another embodiment, the presentinvention is directed to composition as previously described wherein Xrepresents a group which comprises at least two hydroxyl groups. In yetanother embodiment, the present invention is directed to any compositionas previously described wherein X represents a group which comprises atleast one group selected from H, a monohydroxy-substituted organicgroup, and a group having the following structure (V):

R⁴—(CH₂—OH)_(p)  (V)

[0105] wherein the substituent group R⁴ represents

[0106] when p is 2 and the substituent group R³ represents a C₁ to C₄alkylene group, or

[0107] the substituent group R⁴ represents

[0108] when p is 3,

[0109] wherein at least a portion of X represents a group having thestructure (V). In another embodiment, the present invention is directedto any composition as previously described wherein m is 2 and p is 2.

[0110] In one embodiment, the present invention is directed to anycomposition as previously described comprising at least one polysiloxanehaving the structure (II) or (III), wherein, if no curing agent ispresent, and if the at least one polysiloxane is a partial condensate ofa silanol, then less than 70% by weight of the partial condensate is thepartial condensate of CH₃Si(OH)₃. These components used in these variousembodiments can be selected from the coating components discussed above.

[0111] In one embodiment, the present invention is directed tocompositions as previously described wherein the at least onepolysiloxane (a), when added to the other component(s) of thecomposition, is present in the composition in an amount ranging from0.01 to 90 weight percent based on total weight of the resin solids ofthe components which form the composition. In another embodiment, thepresent invention is directed to compositions as previously describedwherein the at least one polysiloxane (a), when added to the othercomponent(s) of the composition, is present in the composition in anamount from at least 2 weight percent based on total weight of the resinsolids of the components which form the composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the at least one polysiloxane (a), whenadded to the other component(s) of the composition, is present in thecomposition in an amount from at least 5 weight percent based on totalweight of the resin solids of the components which form the composition.In yet another embodiment, the present invention is directed tocompositions as previously described wherein the at least onepolysiloxane (a), when added to the other component(s) of thecomposition, is present in the composition in an amount from at least 10weight percent based on total weight of the resin solids of thecomponents which form the composition.

[0112] In one embodiment, the present invention is directed tocompositions as previously described wherein the at least onepolysiloxane (a), when added to the other component(s) of thecomposition, is present in the composition in an amount less than 90weight percent based on total weight of the resin solids of thecomponents which form the composition. In another embodiment, thepresent invention is directed to compositions as previously describedwherein the at least one polysiloxane (a), when added to the othercomponent(s) of the composition, is present in the composition in anamount less than 80 weight percent based on total weight of the resinsolids of the components which form the composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the at least one polysiloxane (a), whenadded to the other component(s) of the composition, is present in thecomposition in an amount less than 65 weight percent based on totalweight of the resin solids of the components which form the composition.In yet another embodiment, the present invention is directed tocompositions as previously described wherein the at least onepolysiloxane (a), when added to the other component(s) of thecomposition, is present in the composition in an amount less than 30weight percent based on total weight of the resin solids of thecomponents which form the composition.

[0113] As used herein “based on total weight of the resin solids” of thecomposition means that the amount of the component added during theformation of the composition is based upon the total weight of the resinsolids (non-volatiles) of the at least one polysiloxane, anyfilm-forming component and any curing agent present during the formationof the coating composition, and any silyl-blocked material present, butnot including the particles, any solvent, or any additive solids such ashindered amine stabilizers, photoinitiators, pigments including extenderpigments and fillers, flow modifiers, catalysts, and UV light absorbers.

[0114] In another embodiment, the present invention is directed to anycomposition as previously described, wherein the at least onepolysiloxane (a) is the reaction product of at least the followingreactants: (i) at least one polysiloxane of the formula (VI):

[0115] wherein each substituent group R, which may be identical ordifferent, represents a group selected from H, OH, a monovalenthydrocarbon group, and mixtures of any of the foregoing; at least one ofthe groups represented by R is H, and n′ ranges from 0 to 100, also canrange from 0 to 10, and can further range from 0 to 5, such that thepercent of SiH content of the polysiloxane ranges from 2 to 50 percent,and can range from 5 to 25 percent; and (ii) at least one molecule whichcomprises at least one functional group selected from a hydroxyl group,a carboxyl group, an isocyanate group, a blocked polyisocyanate group, aprimary amine group, a secondary amine group, an amide group, acarbamate group, a urea group, a urethane group, a vinyl group, anunsaturated ester group such as an acrylate group and a methacrylategroup, a maleimide group, a fumarate group, an onium salt group such asa sulfonium group and an ammonium group, an anhydride group, a hydroxyalkylamide group, and an epoxy group and at least one unsaturated bondcapable of undergoing a hydrosilylation reaction. In another embodiment,the at least one functional group is selected from hydroxyl groups.

[0116] It should be appreciated that the various R groups can be thesame or different, and, in certain embodiments, the R groups will beentirely monovalent hydrocarbon groups or will be a mixture of differentgroups such as monovalent hydrocarbon groups and hydroxyl groups.

[0117] In another embodiment, this reaction product is ungelled. As usedherein, “ungelled” refers to a reaction product that is substantiallyfree of crosslinking and has an intrinsic viscosity when dissolved in asuitable solvent, as determined, for example, in accordance withASTM-D1795 or ASTM-D4243. The intrinsic viscosity of the reactionproduct is an indication of its molecular weight. A gelled reactionproduct, on the other hand, since it is of an extremely high molecularweight, will have an intrinsic viscosity too high to measure. As usedherein, a reaction product that is “substantially free of crosslinking”refers to a reaction product that has a weight average molecular weight(Mw), as determined by gel permeation chromatography, of less than1,000,000.

[0118] It also should be noted that the level of unsaturation containedin reactant (ii) above, can be selected to obtain an ungelled reactionproduct. In other words, when a polysiloxane containing silicon hydride(i) having a higher average value of Si—H functionality is used,reactant (ii) can have a lower level of unsaturation. For example, thepolysiloxane containing silicon hydride (i) can be a low molecularweight material where n′ ranges from 0 to 5 and the average value ofSi—H functionality is two or less. In this case, reactant (ii) cancontain two or more unsaturated bonds capable of undergoinghydrosilylation reaction without the occurrence of gelation.

[0119] Nonlimiting examples of polysiloxanes containing silicon hydride(i) include 1,1,3,3-tetramethyl disiloxane where n′ is 0 and the averageSi—H functionality is two; and polymethyl polysiloxane containingsilicon hydride, where n′ ranges from 4 to 5 and the average Si—Hfunctionality is approximately two, such as is commercially availablefrom BASF Corporation as MASILWAX BASE®.

[0120] Materials for use as reactant (ii) above can include hydroxylfunctional group-containing allyl ethers such as those selected fromtrimethylolpropane monoallyl ether, pentaerythritol monoallyl ether,trimethylolpropane diallyl ether, polyoxyalkylene alcohols such aspolyethoxylated alcohol, polypropoxylated alcohol, and polybutoxylatedalcohol, undecylenic acid-epoxy adducts, allyl glycidyl ether-carboxylicacid adducts, and mixtures of any of the foregoing. Mixtures of hydroxylfunctional polyallyl ethers with hydroxyl functional monoallyl ethers orallyl alcohols are suitable as well. In certain instances, reactant (ii)can contain at least one unsaturated bond in a terminal position.Reaction conditions and the ratio of reactants (i) and (ii) are selectedso as to form the desired functional group.

[0121] The hydroxyl functional group-containing polysiloxane (a) can beprepared by reacting a polysiloxane containing hydroxyl functionalgroups with an anhydride to form the half-ester acid group underreaction conditions that favor only the reaction of the anhydride andthe hydroxyl functional groups, and avoid further esterification fromoccurring. Nonlimiting examples of suitable anhydrides includehexahydrophthalic anhydride, methyl hexahydrophthalic anhydride,phthalic anhydride, trimellitic anhydride, succinic anhydride,chlorendic anhydride, alkenyl succinic anhydride, and substitutedalkenyl anhydrides such as octenyl succinic anhydride, and mixtures ofany of the foregoing.

[0122] The half-ester group-containing reaction product thus preparedcan be further reacted with a monoepoxide to form a polysiloxanecontaining at least one secondary hydroxyl group. Nonlimiting examplesof suitable monoepoxides are phenyl glycidyl ether, n-butyl glycidylether, cresyl glycidyl ether, isopropyl glycidyl ether, glycidylversatate, for example, CARDURA E available from Shell Chemical Co., andmixtures of any of the foregoing.

[0123] In another embodiment, the present invention is directed tocompositions as previously described wherein the at least onepolysiloxane (a) is a carbamate functional group-containing polysiloxanewhich comprises the reaction product of at least the followingreactants:

[0124] (i) at least one polysiloxane containing silicon hydride ofstructure (VI) above where R and n′ are as described above for thatstructure;

[0125] (ii) at least one hydroxyl functional group-containing materialhaving one or more unsaturated bonds capable of undergoinghydrosilylation reaction as described above; and

[0126] (iii) at least one low molecular weight carbamate functionalmaterial, comprising the reaction product of an alcohol or glycol etherand a urea.

[0127] Examples of such “low molecular weight carbamate functionalmaterial” include, but are not limited to, alkyl carbamate and hexylcarbamates, and glycol ether carbamates described in U.S. Pat. Nos.5,922,475 and 5,976,701, which are incorporated herein by reference.

[0128] The carbamate functional groups can be incorporated into thepolysiloxane by reacting the hydroxyl functional group-containingpolysiloxane with the low molecular weight carbamate functional materialvia a “transcarbamoylation” process. The low molecular weight carbamatefunctional material, which can be derived from an alcohol or glycolether, can react with free hydroxyl groups of a polysiloxane polyol,that is, material having an average of two or more hydroxyl groups permolecule, yielding a carbamate functional polysiloxane (a) and theoriginal alcohol or glycol ether. Reaction conditions and the ratio ofreactants (i), (ii) and (iii) are selected so as to form the desiredgroups.

[0129] The low molecular weight carbamate functional material can beprepared by reacting the alcohol or glycol ether with urea in thepresence of a catalyst such as butyl stannoic acid. Nonlimiting examplesof suitable alcohols include lower molecular weight aliphatic,cycloaliphatic and aromatic alcohols, for example, methanol, ethanol,propanol, butanol, cyclohexanol, 2-ethylhexanol, and 3-methylbutanol.Nonlimiting examples of suitable glycol ethers include ethylene glycolmethyl ether, and propylene glycol methyl ether. The incorporation ofcarbamate functional groups into the polysiloxane also can be achievedby reacting isocyanic acid with free hydroxyl groups of thepolysiloxane.

[0130] As aforementioned, in addition to or in lieu of hydroxyl orcarbamate functional groups, the at least one polysiloxane (a) cancontain one or more other reactive functional groups such as carboxylgroups, isocyanate groups, blocked isocyanate groups, carboxylategroups, primary or secondary amine groups, amide groups, urea groups,urethane groups, epoxy groups, and mixtures of any of the foregoing.

[0131] When at least one polysiloxane (a) contains carboxyl functionalgroups, the at least one polysiloxane (a) can be prepared by reacting atleast one polysiloxane containing hydroxyl functional groups asdescribed above with a polycarboxylic acid or anhydride. Nonlimitingexamples of polycarboxylic acids suitable for use include adipic acid,succinic acid, and dodecanedioic acid. Nonlimiting examples of suitableanhydrides include those described above. Reaction conditions and theratio of reactants are selected so as to form the desired functionalgroups.

[0132] In the case where at least one polysiloxane (a) contains one ormore isocyanate functional groups, the at least one polysiloxane (a) canbe prepared by reacting at least one polysiloxane containing hydroxylfunctional groups as described above with a polyisocyanate, such as adiisocyanate. Nonlimiting examples of suitable polyisocyanates includealiphatic polyisocyanates, such as aliphatic diisocyanates, for example,1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate;cycloaliphatic polyisocyanates, for example, 1,4-cyclohexyldiisocyanate, isophorone diisocyanate, and α,α-xylylene diisocyanate;and aromatic polyisocyanates, for example, 4,4′-diphenylmethanediisocyanate, 1,3-phenylene diisocyanate, and tolylene diisocyanate.These and other suitable polyisocyanates are described in more detail inU.S. Pat. No. 4,046,729, at column 5, line 26 to column 6, line 28,incorporated herein by reference. Reaction conditions and the ratio ofreactants are selected so as to form the desired functional groups.

[0133] The substituent group X in structure (IV) can comprise apolymeric urethane or urea-containing material which is terminated withisocyanate, hydroxyl, primary or secondary amine functional groups, ormixtures of any of the foregoing. When the substituent group X comprisessuch functional groups, the at least one polysiloxane (a) can be thereaction product of at least one polysiloxane polyol as described above,one or more polyisocyanates and, optionally, one or more compoundshaving at least two active hydrogen atoms per molecule selected fromhydroxyl groups, primary amine groups, and secondary amine groups.

[0134] Nonlimiting examples of suitable polyisocyanates are thosedescribed above. Nonlimiting examples of compounds having at least twoactive hydrogen atoms per molecule include polyols and polyaminescontaining primary or secondary amine groups.

[0135] Nonlimiting examples of suitable polyols include polyalkyleneether polyols, including thio ethers; polyester polyols, includingpolyhydroxy polyesteramides; and hydroxyl-containing polycaprolactonesand hydroxy-containing acrylic interpolymers. Also useful are polyetherpolyols formed from the oxyalkylation of various polyols, for example,glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A, and thelike, or higher polyols such as trimethylolpropane, pentaerythritol andthe like. Polyester polyols also can be used. These and other suitablepolyols are described in U.S. Pat. No. 4,046,729 at column 7, line 52 tocolumn 8, line 9; column 8, line 29 to column 9, line 66; and U.S. Pat.No. 3,919,315 at column 2, line 64 to column 3, line 33, bothincorporated herein by reference.

[0136] Nonlimiting examples of suitable polyamines include primary orsecondary diamines or polyamines in which the groups attached to thenitrogen atoms can be saturated or unsaturated, aliphatic, alicyclic,aromatic, aromatic-substituted-aliphatic, aliphatic-substituted-aromaticand heterocyclic. Exemplary suitable aliphatic and alicyclic diaminesinclude 1,2-ethylene diamine, 1,2-porphylene diamine, 1,8-octanediamine, isophorone diamine, propane-2,2-cyclohexyl amine, and the like.Suitable aromatic diamines include phenylene diamines and the toluenediamines, for example, o-phenylene diamine and p-tolylene diamine. Theseand other suitable polyamines are described in detail in U.S. Pat. No.4,046,729 at column 6, line 61 to column 7, line 26, incorporated hereinby reference.

[0137] In one embodiment, the substituent group X of the structure (IV)can comprise a polymeric ester-containing group which is terminated withhydroxyl or carboxylic acid functional groups. When X is such a group,at least one polysiloxane (a) can be the reaction product of one or morepolysiloxane polyols as described above, one or more materials having atleast one carboxylic acid functional group, and one or more organicpolyols. Nonlimiting suitable examples of materials having at least onecarboxylic acid functional group include carboxylic acidgroup-containing polymers well-known in the art, for example, carboxylicacid group-containing acrylic polymers, polyester polymers, andpolyurethane polymers, such as those described in U.S. Pat. No.4,681,811. Nonlimiting examples of suitable organic polyols includethose described above.

[0138] To form the at least one polysiloxane (a) containing epoxygroups, at least one polysiloxane containing hydroxyl functional groupsas described above can be further reacted with a polyepoxide. Thepolyepoxide can be an aliphatic or cycloaliphatic polyepoxide ormixtures of any of the foregoing. Nonlimiting examples of polyepoxidessuitable for use include epoxy functional acrylic copolymers preparedfrom at least one ethylenically unsaturated monomer having at least oneepoxy group, for example glycidyl (meth)acrylate and allyl glycidylether, and one or more ethylenically unsaturated monomers which have noepoxy functionality. The preparation of such epoxy functional acryliccopolymers is described in detail in U.S. Pat. No. 4,681,811 at column4, line 52 to column 5, line 50, incorporated herein by reference.Reaction conditions and the ratio of reactants are selected so as toform the desired functional groups.

[0139] In one embodiment, the present invention is directed tocompositions as previously described wherein the composition comprises aplurality of particles. In another embodiment, the present invention isdirected to compositions as previously described wherein the particleshave an average particle size less than 50 microns prior toincorporation into the composition. In another embodiment, the presentinvention is directed to compositions as previously described whereinthe particles have an average particle size ranging from 1 to less than1000 nanometers prior to incorporation into the composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the particles have an average particle sizeranging from 1 to 100 nanometers prior to incorporation into thecomposition.

[0140] In another embodiment, the present invention is directed tocompositions as previously described wherein the particles have anaverage particle size ranging from 5 to 50 nanometers prior toincorporation into the composition. In another embodiment, the presentinvention is directed to compositions as previously described whereinthe particles have an average particle size ranging from 5 to 25nanometers prior to incorporation into the composition. The particlesize may range from any combination of these values inclusive of therecited values.

[0141] In an embodiment where the average particle size of the particlesis greater than one micron, the average particle size can be measuredaccording to known laser scattering techniques. For example, the averageparticle size of such particles is measured using a Horiba Model LA 900laser diffraction particle size instrument, which uses a helium-neonlaser with a wave length of 633 nm to measure the size of the particlesand assumes the particle has a spherical shape, i.e., the “particlesize” refers to the smallest sphere that will completely enclose theparticle.

[0142] In an embodiment of the present invention wherein the size of theparticles is less than or equal to one micron, the average particle sizecan be determined by visually examining an electron micrograph of atransmission electron microscopy (“TEM”) image, measuring the diameterof the particles in the image, and calculating the average particle sizebased on the magnification of the TEM image. One of ordinary skill inthe art will understand how to prepare such a TEM image, and adescription of one such method is disclosed in the examples set forthbelow. In one nonlimiting embodiment of the present invention, a TEMimage with 105,000× magnification is produced, and a conversion factoris obtained by dividing the magnification by 1000. Upon visualinspection, the diameter of the particles is measured in millimeters,and the measurement is converted to nanometers using the conversionfactor. The diameter of the particle refers to the smallest diametersphere that will completely enclose the particle.

[0143] The shape (or morphology) of the particles can vary dependingupon the specific embodiment of the present invention and its intendedapplication. For example generally spherical morphologies (such as solidbeads, microbeads, or hollow spheres), can be used, as well as particlesthat are cubic, platy, or acicular (elongated or fibrous). Additionally,the particles can have an internal structure that is hollow, porous orvoid free, or a combination of any of the foregoing, e.g., a hollowcenter with porous or solid walls. For more information on suitableparticle characteristics see H. Katz et al. (Ed.), Handbook of Fillersand Plastics (1987) at pages 9-10, which are specifically incorporatedby reference herein.

[0144] It will be recognized by one skilled in the art that mixtures ofone or more particles having different average particle sizes can beincorporated into the compositions in accordance with the presentinvention to impart the desired properties and characteristics to thecompositions. For example, particles of varying sizes can be used in thecompositions according to the present invention.

[0145] The particles can be formed from materials selected frompolymeric and nonpolymeric inorganic materials, polymeric andnonpolymeric organic materials, composite materials, and mixtures of anyof the foregoing. As used herein, the term “polymeric inorganicmaterial” means a polymeric material having a backbone repeat unit basedon an element or elements other than carbon. For more information seeJames Mark et al., Inorganic Polymers, Prentice Hall Polymer Science andEngineering Series, (1992) at page 5, which is specifically incorporatedby reference herein. As used herein, the term “polymeric organicmaterials” means synthetic polymeric materials, semisynthetic polymericmaterials and natural polymeric materials, all of which have a backbonerepeat unit based on carbon.

[0146] An “organic material,” as used herein, means carbon containingcompounds wherein the carbon is typically bonded to itself and tohydrogen, and often to other elements as well, and excludes binarycompounds such as the carbon oxides, the carbides, carbon disulfide,etc.; such ternary compounds as the metallic cyanides, metalliccarbonyls, phosgene, carbonyl sulfide, etc.; and carbon-containing ioniccompounds such as metallic carbonates, for example, calcium carbonateand sodium carbonate. See R. Lewis, Sr., Hawley's Condensed ChemicalDictionary, (12th Ed. 1993) at pages 761-762, and M. Silberberg,Chemistry The Molecular Nature of Matter and Change (1996) at page 586,which are specifically incorporated by reference herein.

[0147] As used herein, the term “inorganic material” means any materialthat is not an organic material.

[0148] As used herein, the term “composite material” means a combinationof two or more differing materials. The particles formed from compositematerials generally have a hardness at their surface that is differentfrom the hardness of the internal portions of the particle beneath itssurface. More specifically, the surface of the particle can be modifiedin any manner well known in the art, including, but not limited to,chemically or physically changing its surface characteristics usingtechniques known in the art.

[0149] For example, a particle can be formed from a primary materialthat is coated, clad or encapsulated with one or more secondarymaterials to form a composite particle that has a softer surface. In yetanother alternative embodiment, particles formed from compositematerials can be formed from a primary material that is coated, clad orencapsulated with a different form of the primary material. For moreinformation on particles useful in the present invention, see G. Wypych,Handbook of Fillers, 2nd Ed. (1999) at pages 15-202, which arespecifically incorporated by reference herein.

[0150] The particles suitable for use in the compositions of theinvention can comprise inorganic elements or compounds known in the art.Suitable particles can be formed from ceramic materials, metallicmaterials, and mixtures of any of the foregoing. Suitable ceramicmaterials comprise metal oxides, metal nitrides, metal carbides, metalsulfides, metal silicates, metal borides, metal carbonates, and mixturesof any of the foregoing. Specific, nonlimiting examples of metalnitrides are, for example, boron nitride; specific, nonlimiting examplesof metal oxides are, for example, zinc oxide; nonlimiting examples ofsuitable metal sulfides are, for example, molybdenum disulfide, tantalumdisulfide, tungsten disulfide, and zinc sulfide; nonlimiting suitableexamples of metal silicates are, for example, aluminum silicates andmagnesium silicates such as vermiculite.

[0151] The particles can comprise, for example, a core of essentially asingle inorganic oxide such as silica in colloidal, fumed, or amorphousform, alumina or colloidal alumina, titanium dioxide, cesium oxide,yttrium oxide, colloidal yttria, zirconia, e.g., colloidal or amorphouszirconia, and mixtures of any of the foregoing; or an inorganic oxide ofone type upon which is deposited an organic oxide of another type. Itshould be understood that when the composition of the invention isemployed as a transparent topcoat, for example, as a clearcoat in amulti-component composite coating composition, particles should notseriously interfere with the optical properties of the composition. Asused herein, “transparent” means that the cured coating has a BYK Hazeindex of less than 50 as measured using a BYK/Haze Gloss instrument.

[0152] Nonpolymeric, inorganic materials useful in forming the particlesof the present invention comprise inorganic materials selected fromgraphite, metals, oxides, carbides, nitrides, borides, sulfides,silicates, carbonates, sulfates, and hydroxides. A nonlimiting exampleof a useful inorganic oxide is zinc oxide. Nonlimiting examples ofsuitable inorganic sulfides include molybdenum disulfide, tantalumdisulfide, tungsten disulfide, and zinc sulfide. Nonlimiting examples ofuseful inorganic silicates include aluminum silicates and magnesiumsilicates, such as vermiculite. Nonlimiting examples of suitable metalsinclude molybdenum, platinum, palladium, nickel, aluminum, copper, gold,iron, silver, alloys, and mixtures of any of the foregoing.

[0153] In one embodiment, the present invention is directed tocompositions as previously described wherein the particles are selectedfrom fumed silica, amorphous silica, colloidal silica, alumina,colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide,colloidal yttria, zirconia, colloidal zirconia, and mixtures of any ofthe foregoing. In another embodiment, the present invention is directedto compositions as previously described wherein the particles includecolloidal silica. In one embodiment, these materials can be surfacetreated, the surface treatment resulting in particles which aresubstantially nonreactive with the at least one reactive functionalgroup of the at least one polysiloxane and with the at least onefunctional group of the at least one reactant.

[0154] The composition can comprise precursors suitable for formingsilica particles in situ by a sol-gel process. The composition accordingto the present invention can comprise alkoxy silanes which can behydrolyzed to form silica particles in situ. For example,tetraethylortho silicate can be hydrolyzed with an acid such ashydrochloric acid and condensed to form silica particles. Other usefulparticles include surface-modified silicas such as are described in U.S.Pat. No. 5,853,809 at column 6, line 51 to column 8, line 43, which isincorporated herein by reference.

[0155] In one embodiment of the present invention, the particles have ahardness value greater than the hardness value of materials that canabrade a polymeric coating or a polymeric substrate. Examples ofmaterials that can abrade the polymeric coating or polymeric substrateinclude, but are not limited to, dirt, sand, rocks, glass, carwashbrushes, and the like. The hardness values of the particles and thematerials that can abrade the polymeric coating or polymeric substratecan be determined by any conventional hardness measurement method, suchas Vickers or Brinell hardness, but can also be determined according tothe original Mohs' hardness scale which indicates the relative scratchresistance of the surface of a material on a scale of one to ten. TheMohs' hardness values of several nonlimiting examples of particlesformed from inorganic materials suitable for use in the presentinvention are given in Table A below. TABLE A Particle material Mohs'hardness (original scale) Boron nitride 2¹ Graphite 0.5-1² Molybdenumdisulfide 1³ Talc 1-1.5⁴ Mica 2.8-3.2⁵ Kaolinite 2.0-2.56 Gypsum 1.6-2⁷Calcite (calcium carbonate) 3⁸ Calcium fluoride 4⁹ Zinc oxide 4.5¹⁰Aluminum 2.5¹¹ Copper 2.5-3¹² Iron 4-5¹³ Gold 2.5-3¹⁴ Nickel 5¹⁵Palladium 4.8¹⁶ Platinum 4.3¹⁷ Silver 2.5-4¹⁸ Zinc sulfide 3.5-4¹⁹ #incorporated by reference. # at page F-22. # at page 793, which ishereby incorporated by reference. # which is hereby incorporated byreference. # which is hereby incorporated by reference. # (71^(st)Ed1990) at page

[0156] In one embodiment, the Mohs' hardness value of the particles isgreater than 5. In certain embodiments, the Mohs' hardness value of theparticles, such as silica, is greater than 6.

[0157] As mentioned above, the Mohs' hardness scale relates to theresistance of a material to scratching. The present invention thereforefurther contemplates particles that have a hardness at their surfacethat is different from the hardness of the internal portions of theparticle beneath its surface. More specifically, and as discussed above,the surface of the particle can be modified in any manner well known inthe art, including, but not limited to, chemically changing theparticle's surface characteristics using techniques known in the artsuch that the surface hardness of the particle is greater the hardnessof the materials that can abrade the polymeric coating or polymericsubstrate while the hardness of the particle beneath the surface is lessthan the hardness of the materials that can abrade the polymeric coatingor polymeric substrate.

[0158] As another alternative, a particle can be formed from a primarymaterial that is coated, clad or encapsulated with one or more secondarymaterials to form a composite material that has a harder surface.Alternatively, a particle can be formed from a primary material that iscoated, clad or encapsulated with a differing form of the primarymaterial to form a composite material that has a harder surface.

[0159] In one example, and without limiting the present invention, aninorganic particle formed from an inorganic material such as siliconcarbide or aluminum nitride can be provided with a silica, carbonate ornanoclay coating to form a useful composite particle. In anothernonlimiting example, a silane coupling agent with alkyl side chains caninteract with the surface of an inorganic particle formed from aninorganic oxide to provide a useful composite particle having a “softer”surface. Other examples include cladding, encapsulating or coatingparticles formed from nonpolymeric or polymeric materials with differingnonpolymeric or polymeric materials. A specific nonlimiting example ofsuch composite particles is DUALITE™, which is a synthetic polymericparticle coated with calcium carbonate that is commercially availablefrom Pierce and Stevens Corporation of Buffalo, N.Y.

[0160] In one nonlimiting embodiment of the invention, the particles areformed from solid lubricant materials. As used herein, the term “solidlubricant” means any solid used between two surfaces to provideprotection from damage during relative movement or to reduce frictionand wear. In one embodiment, the solid lubricants are inorganic solidlubricants. As used herein, “inorganic solid lubricant” means that thesolid lubricants have a characteristic crystalline habit which causesthem to shear into thin, flat plates which readily slide over oneanother and thus produce an antifriction lubricating effect. See R.Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) atpage 712, which is specifically incorporated by reference herein.Friction is the resistance to sliding one solid over another. F. Clauss,Solid Lubricants and Self-Lubricating Solids (1972) at page 1, which isspecifically incorporated by reference herein.

[0161] In one nonlimiting embodiment of the invention, the particleshave a lamellar structure. Particles having a lamellar structure arecomposed of sheets or plates of atoms in hexagonal array, with strongbonding within the sheet and weak van der Waals bonding between sheets,providing low shear strength between sheets. A nonlimiting example of alamellar structure is a hexagonal crystal structure. Inorganic solidparticles having a lamellar fullerene (i.e., buckyball) structure alsoare useful in the present invention.

[0162] Nonlimiting examples of suitable materials having a lamellarstructure that are useful in forming the particles of the presentinvention include boron nitride, graphite, metal dichalcogenides, mica,talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide, andmixtures of any of the foregoing. Suitable metal dichalcogenides includemolybdenum disulfide, molybdenum diselenide, tantalum disulfide,tantalum diselenide, tungsten disulfide, tungsten diselenide, andmixtures of any of the foregoing.

[0163] The particles can be formed from nonpolymeric, organic materials.Nonlimiting examples of nonpolymeric, organic materials useful in thepresent invention include, but are not limited to, stearates (such aszinc stearate and aluminum stearate), diamond, carbon black, andstearamide.

[0164] The particles can be formed from inorganic polymeric materials.Nonlimiting examples of useful inorganic polymeric materials includepolyphosphazenes, polysilanes, polysiloxane, polygeremanes, polymericsulfur, polymeric selenium, silicones, and mixtures of any of theforegoing. A specific, nonlimiting example of a particle formed from aninorganic polymeric material suitable for use in the present inventionis TOSPEARL²⁰, which is a particle formed from cross-linked siloxanesand is commercially available from Toshiba Silicones Company, Ltd. ofJapan.

[0165] The particles can be formed from synthetic, organic polymericmaterials. Nonlimiting examples of suitable organic polymeric materialsinclude, but are not limited to, thermoset materials and thermoplasticmaterials. As used herein, a “thermoplastic” material is a material thatsoftens when exposed to heat and retums to its original condition whencooled to room temperature. Nonlimiting examples of suitablethermoplastic materials include thermoplastic polyesters such aspolyethylene terephthalate, polybutylene terephthalate, and polyethylenenaphthalate, polycarbonates, polyolefins such as polyethylene,polypropylene, and polyisobutene, acrylic polymers such as copolymers ofstyrene and an acrylic acid monomer, and polymers containingmethacrylate, polyamides, thermoplastic polyurethanes, vinyl polymers,and mixtures of any of the foregoing.

[0166] Nonlimiting examples of suitable thermoset materials includethermoset polyesters, vinyl esters, epoxy materials, phenolics,aminoplasts, thermoset polyurethanes, and mixtures of any of theforegoing. A specific, nonlimiting example of a synthetic polymericparticle formed from an epoxy material is an epoxy microgel particle. Asused herein, a “thermoset” material is a material that materialsolidifies or “sets” irreversibly when heated. A thermoset material hasformed a crosslinked network. As used herein, a polymeric material is“crosslinked” if it at least partially forms a polymeric network. Oneskilled in the art will understand that the presence and degree ofcrosslinking (crosslink density) can be determined by a variety ofmethods, such as dynamic mechanical thermal analysis (DMTA) using a TAInstruments DMA 2980 DMTA analyzer conducted under nitrogen such as isdescribed above. This method determines the glass transition temperatureand crosslink density of free films of coatings or polymers. Thesephysical properties of a cured material are related to the structure ofthe crosslinked network.

[0167] The particles also can be hollow particles formed from materialsselected from polymeric and nonpolymeric inorganic materials, polymericand nonpolymeric organic materials, composite materials, and mixtures ofany of the foregoing. Nonlimiting examples of suitable materials fromwhich the hollow particles can be formed are described above.

[0168] In one embodiment, the present invention is directed tocompositions as previously described wherein the particles, when addedto the other components of the composition, are present in thecomposition in an amount ranging from 0.01 to 75 weight percent based ontotal weight of the resin solids of the components which form thecomposition. In another embodiment, the present invention is directed tocompositions as previously described wherein the particles, when addedto the other components of the composition, are present in thecomposition in an amount of at least 0.1 weight percent based on totalweight of the resin solids of the components which form the composition.In another embodiment, the present invention is directed to compositionsas previously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount greater than 0.5 weight percent based on total weight of theresin solids of the components which form the composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount greater than 5 weight percent based on total weight of the resinsolids of the components which form the composition.

[0169] In yet another embodiment, the present invention is directed tocompositions as previously described wherein, the particles, when addedto the other components of the composition, are present in thecomposition in an amount less than 75 weight percent based on totalweight of the resin solids of the components which form the composition.In a further embodiment, the present invention is directed tocompositions as previously described wherein the particles, when addedto the other components of the composition, are present in thecomposition in an amount less than 50 weight percent based on totalweight of the resin solids of the components which form the composition.In another embodiment, the present invention is directed to compositionsas previously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount less than 20 weight percent based on total weight of the resinsolids of the components which form the composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount less than 10 weight percent based on total weight of the resinsolids of the components which form the composition. The amount ofparticles may range between any combination of these values inclusive ofthe recited values.

[0170] Prior to incorporation, one class of particles which can be usedaccording to the present invention includes sols, such as an organosol,of the particles. These sols can be of a wide variety of small-particle,colloidal silicas having an average particle size in ranges such asidentified above.

[0171] at pages 39-44.

[0172] The colloidal silicas can be surface modified during or after theparticles are initially formed, with the resulting particles beingsubstantially nonreactive with the at least one reactive functionalgroup of the at least one polysiloxane and with the at least onefunctional group of the at least one reactant. These surface modifiedsilicas may contain on their surface chemically bonded carbon-containingmoieties, as well as such groups as anhydrous SiO₂ groups and SiOHgroups, various ionic groups physically associated or chemically bondedwithin the surface of the silica, adsorbed organic groups, orcombinations of any of the foregoing, depending on the characteristicsof the particular silica desired. Such surface modified silicas aredescribed in detail in U.S. Pat. No. 4,680,204, which is incorporatedherein by reference.

[0173] Such materials can be prepared by a variety of techniques invarious forms, nonlimiting examples comprise organosols and mixed sols.As used herein the term “mixed sols” is intended to include thosedispersions of colloidal silica in which the dispersing medium comprisesboth an organic liquid and water. Such small particle colloidal silicasare readily available, are essentially colorless and have refractiveindices which permit their inclusion in compositions that, withoutadditional pigments or components known in the art to color or decreasethe transparency of such compositions, result in colorless, transparentcoatings.

[0174] Suitable nonlimiting examples of particles include colloidalsilicas, such as those commercially available from Nissan ChemicalCompany under the trademark ORGANOSILICASOLS™ such as ORGANOSILICASOL™MT-ST, and from Clariant Corporation as HIGHLINK™; colloidal aluminas,such as those commercially available from Nalco Chemical under thetrademark NALCO 8676; and colloidal zirconias, such as thosecommercially available from Nissan Chemical Company under the trademarkHIT-32M®.

[0175] The particles can be incorporated into the compositions of theinvention in the form of a stable dispersion. When the particles are ina colloidal form, the dispersions can be prepared by dispersing theparticles in a carrier under agitation and solvent that is present canbe removed under vacuum at ambient temperatures. In certain embodiments,the carrier can be other than a solvent, such as the surface activeagents described in detail below, including, but not limited to apolysiloxane containing reactive functional groups, including, but notlimited to, the at least one polysiloxane (a).

[0176] Alternatively, the dispersions can be prepared as described inU.S. Pat. Nos. 4,522,958 or 4,526,910, which are incorporated byreference herein. The particles can be “cold-blended” with the at leastone polysiloxane (a) prior to incorporation into the inventivecompositions. Alternatively, the particles can be post-added to anadmixture of any remaining composition components (including, but notlimited to, the at least one polysiloxane (a)) and dispersed thereinusing dispersing techniques well-known in the art.

[0177] When the particles are in other than colloidal form, for example,but not limited to, agglomerate form, the dispersions can be prepared bydispersing the agglomerate in the carrier, for example, but not limitedto, the at least one polysiloxane (a), to stably disperse the particlestherein. Dispersion techniques such as grinding, milling,microfluidizing, ultrasounding, or any other pigment dispersingtechniques well known in the art of coatings formulation can be used.Alternatively, the particles can be dispersed by any other dispersiontechniques known in the art. If desired, the particles in other thancolloidal form can be post-added to an admixture of other compositioncomponents and dispersed therein using any dispersing techniques knownin the art.

[0178] The particles according to the present invention that are appliedto the polymeric substrate or polymeric coating, for example, but notlimited to, the electrodeposited coating, the primer coating, or thetopcoat, can be present in a dispersion, suspension or emulsion in acarrier. Nonlimiting examples of suitable carriers include, but are notlimited to, water, solvents, surfactants, or a mixture of any of theforegoing. Nonlimiting examples of suitable solvents include, but arenot limited to, mineral oil, alcohols such as methanol or butanol,ketones such as methyl amyl ketone, aromatic hydrocarbons such asxylene, glycol ethers such as ethylene glycol monobutyl ether, esters,aliphatics, and mixtures of any of the foregoing.

[0179] As discussed above, besides the at least one polysiloxane (a),the compositions of the present invention can be formed from at leastone reactant comprising at least one functional group that is reactivewith at least one functional group selected from the at least onereactive functional group of the at least one polysiloxane and at leastone functional group of at least one reactant. In one embodiment, the atleast one reactant is selected from at least one curing agent.

[0180] In a further embodiment, the present invention is directed tocompositions as previously described wherein a curing agent is present.This curing agent can be selected from an aminoplast resin, apolyisocyanate, a blocked polyisocyanate compound, a polyepoxide, apolyacid, a polyol, and mixtures of any of the foregoing.

[0181] In another embodiment, the present invention is directed tocompositions as previously described wherein the curing agent is anaminoplast. Aminoplast resins, which comprise phenoplasts, as curingagents for hydroxyl, carboxylic acid, and carbamate functionalgroup-containing materials are well known in the art. Suitableaminoplasts, such as those discussed above, are known to those ofordinary skill in the art. Aminoplasts can be obtained from thecondensation reaction of formaldehyde with an amine or amide.Nonlimiting examples of amines or amides include melamine, urea, orbenzoguanamine. Condensates with other amines or amides can be used; forexample, aldehyde condensates of glycoluril, which give a high meltingcrystalline product useful in powder coatings. While the aldehyde usedis most often formaldehyde, other aldehydes such as acetaldehyde,crotonaidehyde, and benzaldehyde can be used.

[0182] The aminoplast contains imino and methylol groups and in certaininstances at least a portion of the methylol groups are etherified withan alcohol to modify the cure response. Any monohydric alcohol can beemployed for this purpose including methanol, ethanol, n-butyl alcohol,isobutanol, and hexanol.

[0183] Nonlimiting examples of aminoplasts include melamine-, urea-, orbenzoguanamine-formaldehyde condensates, in certain instances monomericand at least partially etherified with one or more alcohols containingfrom one to four carbon atoms. Nonlimiting examples of suitableaminoplast resins are commercially available, for example, from CytecIndustries, Inc. under the trademark CYMEL®, and from Solutia, Inc.under the trademark RESIMENE®.

[0184] In another embodiment, the present invention is directed tocompositions as previously described wherein the curing agent, whenadded to the other components of the composition, is generally presentin an amount ranging from 1 weight percent to 65 weight percent based ontotal weight of the resin solids of the components which form thecomposition, inclusive of the recited values.

[0185] Other curing agents suitable for use include, but are not limitedto, polyisocyanate curing agents. As used herein, the term“polyisocyanate” is intended to include blocked (or capped)polyisocyanates as well as unblocked polyisocyanates. The polyisocyanatecan be an aliphatic or an aromatic polyisocyanate, or a mixture of theforegoing two. Diisocyanates can be used, although higherpolyisocyanates such as isocyanurates of diisocyanates are often used.Higher polyisocyanates also can be used in combination withdiisocyanates. Isocyanate prepolymers, for example, reaction products ofpolyisocyanates with polyols also can be used. Mixtures ofpolyisocyanate curing agents can be used.

[0186] If the polyisocyanate is blocked or capped, any suitablealiphatic, cycloaliphatic, or aromatic alkyl monoalcohol known to thoseskilled in the art can be used as a capping agent for thepolyisocyanate. Other suitable capping agents include oximes andlactams. When used, the polyisocyanate curing agent is typicallypresent, when added to the other components in the composition, in anamount ranging from 5 to 65 weight percent, can be present in an amountranging from 10 to 45 weight percent, and often are present in an amountranging from 15 to 40 percent by weight based on the total weight of theresin solids of the components which form the composition, inclusive ofthe recited values.

[0187] Other useful curing agents comprise blocked isocyanate compoundssuch as the tricarbamoyl triazine compounds described in detail in U.S.Pat. No. 5,084,541, which is incorporated by reference herein. Whenused, the blocked isocyanate curing agent can be present, when added tothe other components in the composition, in an amount ranging up to 20weight percent, and can be present in an amount ranging from 1 to 20weight percent, based on the total weight of the resin solids of thecomponents which form the composition, inclusive of the recited values.

[0188] Anhydrides as curing agents for hydroxyl functionalgroup-containing materials also are well known in the art and can beused in the present invention. Nonlimiting examples of anhydridessuitable for use as curing agents in the compositions of the inventioninclude those having at least two carboxylic acid anhydride groups permolecule which are derived from a mixture of monomers comprising anethylenically unsaturated carboxylic acid anhydride and at least onevinyl co-monomer, for example, styrene, alpha-methyl styrene, vinyltoluene, and the like. Nonlimiting examples of suitable ethylenicallyunsaturated carboxylic acid anhydrides include maleic anhydride,citraconic anhydride, and itaconic anhydride. Alternatively, theanhydride can be an anhydride adduct of a diene polymer such asmaleinized polybutadiene or a maleinized copolymer of butadiene, forexample, a butadiene/styrene copolymer. These and other suitableanhydride curing agents are described in U.S. Pat. No. 4,798,746 atcolumn 10, lines 16-50; and in U.S. Pat. No. 4,732,790 at column 3,lines 41-57, both of which are incorporated herein by reference.

[0189] Polyepoxides as curing agents for carboxylic acid functionalgroup-containing materials are well known in the art. Nonlimitingexamples of polyepoxides suitable for use in the compositions of thepresent invention comprise polyglycidyl ethers of polyhydric phenols andof aliphatic alcohols, which can be prepared by etherification of thepolyhydric phenol, or aliphatic alcohol with an epihalohydrin such asepichlorohydrin in the presence of alkali. These and other suitablepolyepoxides are described in U.S. Pat. No. 4,681,811 at column 5, lines33 to 58, which is incorporated herein by reference.

[0190] Suitable curing agents for epoxy functional group-containingmaterials comprise polyacid curing agents, such as the acidgroup-containing acrylic polymers prepared from an ethylenicallyunsaturated monomer containing at least one carboxylic acid group and atleast one ethylenically unsaturated monomer which is free fromcarboxylic acid groups. Such acid functional acrylic polymers can havean acid number ranging from 30 to 150. Acid functional group-containingpolyesters can be used as well. The above-described polyacid curingagents are described in further detail in U.S. Pat. No. 4,681,811 atcolumn 6, line 45 to column 9, line 54, which is incorporated herein byreference.

[0191] Also well known in the art as curing agents for isocyanatefunctional group-containing materials are polyols, that is, materialshaving two or more hydroxyl groups per molecule. Nonlimiting examples ofsuch materials suitable for use in the compositions of the inventioninclude polyalkylene ether polyols, including thio ethers; polyesterpolyols, including polyhydroxy polyesteramides; and hydroxyl-containingpolycaprolactones and hydroxy-containing acrylic interpolymers. Alsouseful are polyether polyols formed from the oxyalkylation of variouspolyols, for example, glycols such as ethylene glycol, 1,6-hexanediol,Bisphenol A and the like, or higher polyols such as trimethylolpropane,pentaerythritol, and the like. Polyester polyols also can be used. Theseand other suitable polyol curing agents are described in U.S. Pat. No.4,046,729 at column 7, line 52 to column 8, line 9; column 8, line 29 tocolumn 9, line 66; and U.S. Pat. No. 3,919,315 at column 2, line 64 tocolumn 3, line 33, both of which are incorporated herein by reference.

[0192] Polyamines also can be used as curing agents for isocyanatefunctional group-containing materials. Nonlimiting examples of suitablepolyamine curing agents include primary or secondary diamines orpolyamines in which the radicals attached to the nitrogen atoms can besaturated or unsaturated, aliphatic, alicyclic, aromatic,aromatic-substituted-aliphatic, aliphatic-substituted—aromatic, andheterocyclic. Nonlimiting examples of suitable aliphatic and alicyclicdiamines include 1,2-ethylene diamine, 1,2-porphylene diamine,1.8-octane diamine, isophorone diamine, propane-2,2-cyclohexyl amine,and the like. Nonlimiting examples of suitable aromatic diamines includephenylene diamines and the toluene diamines, for example, o-phenylenediamine and p-tolylene diamine. These and other suitable polyaminesdescribed in detail in U.S. Pat. No. 4,046,729 at column 6, line 61 tocolumn 7, line 26, which is incorporated herein by reference.

[0193] When desired, appropriate mixtures of curing agents may be used.It should be mentioned that compositions can be formulated as aone-component composition where a curing agent such as an aminoplastresin or a blocked isocyanate compound such as those described above isadmixed with other composition components. The one-component compositioncan be storage stable as formulated. Alternatively, compositions can beformulated as a two-component composition where a polyisocyanate curingagent such as those described above can be added to a pre-formedadmixture of the other composition components just prior to application.The pre-formed admixture can comprise curing agents such as aminoplastresins or blocked isocyanate compounds such as those described above.

[0194] In another embodiment in which the coating is cured by actinicradiation or the combination of actinic radiation and thermal energy,the components from which the coating composition are formed further cancomprise at least one curing agent which is a photoinitiator orphotosensitizer which provides free radicals or cations to initiate thepolymerization process. Useful photoinitiators have an adsorption in therange of 150 to 2,000 nm. Non-limiting examples of usefulphotoinitiators include benzoin, benzophenone, hydroxy benzophenone,anthraquinone, thioxanthone, substituted benzoins such as butyl isomersof benzoin ethers, α,α-diethoxyacetophenone,α,α-dimethoxy-α-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl propane1-one and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide.

[0195] In an alternative embodiment, the reactant can comprise at leastone material which has at least one reactive functional group which isblocked with a silyl group. This silyl-blocked material is differentfrom the polysiloxane (a) discussed above. Hydrolysis of the silyl groupregenerates the reactive functional group on the material which isavailable for further reaction with the curing agent.

[0196] In one embodiment, the silyl blocking groups can have thefollowing structure (IX):

[0197] wherein each R₁, R₂ and R₃, which may be identical or different,represents an alkyl group having from 1 to 18 carbon atoms, a phenylgroup or an allyl group.

[0198] Non-limiting examples of suitable functional groups which can beblocked by the silyl group comprise hydroxyl groups, carbamate groups,carboxyl groups, amide groups and mixtures thereof. In one embodiment,the functional groups are hydroxyl groups.

[0199] Non-limiting examples of suitable compounds which can be reactedwith the functional group to form the silyl group comprisehexamethyldisilazane, trimethylchlorosilane, trimethylsilyldiethylamine,t-butyl dimethylsilyl chloride, diphenyl methylsilyl chloride,hexamethyl disilylazide, hexamethyl disiloxane, trimethylsilyl triflate,hexamethyldisilyl acetamide, N,N′-bis[trimethylsilyl]-urea, and mixturesof any of the foregoing. In one embodiment, hexamethyldisilazane is usedto form the silyl group.

[0200] Further examples of suitable compounds for silylation reactions,and suitable reaction conditions and reagents for trimethylsilylationreactions are discussed in Example 28 below and in T. Greene et al.,Protective Groups in Organic Synthesis, (2d. ed. 1991) at pages 68-86and 261-263, which are incorporated herein by reference.

[0201] The backbone of the material can be a compound which comprises atleast one linkage selected from an ester linkage, a urethane linkage, aurea linkage, a siloxane linkage, an amide linkage and an ether linkageor a polymer such as a polyester, an acrylic polymer, a polyurethane, apolyether, a polyurea, a polyamide and copolymers of any of theforegoing.

[0202] Suitable compounds or polymers having at least one ester linkageand at least one reactive functional group include half-esters formedfrom reacting at least one polyol with at least one anhydride. Thehalf-esters are suitable because they are of relatively low molecularweight and are quite reactive with epoxy functionality.

[0203] The half-ester may be obtained by reaction between a polyol and a1,2-anhydride under conditions sufficient to ring open the anhydrideforming the half-ester with substantially no polyesterificationoccurring. Such reaction products are of relatively low molecular weightwith narrow molecular weight distributions and low viscosity. By“substantially no polyesterification occurring” means that the carboxylgroups formed by the reaction of the anhydride are not furtheresterified by the polyol in a recurring manner. This means thatgenerally less than 10, and typically less than 5 percent by weight ofhigh molecular weight polyester is formed.

[0204] The 1,2-anhydride and polyol generally are mixed together and thereaction is conducted in the presence of an inert atmosphere such asnitrogen and a solvent such as a ketone or aromatic hydrocarbon todissolve the solid ingredients and/or lower the viscosity of thereaction mixture.

[0205] For the desired ring opening reaction and half-ester formation, a1,2-dicarboxylic anhydride is used. Reaction of a polyol with acarboxylic acid instead of an anhydride would require esterification bycondensation and elimination water would have to be removed bydistillation. Under these conditions, this would promote undesiredpolyesterification. Also, the reaction temperature is generally low,i.e., less than 135° C. and can range from 70° C. to 135° C. The time ofreaction can vary somewhat depending upon the temperature of reaction,and generally ranges from 10 minutes to 24 hours.

[0206] The equivalent ratio of anhydride to hydroxyl on the polyol canbe at least 0.8:1 (the anhydride being considered monofunctional) toobtain maximum conversion to the desired half-ester. Ratios less than0.8:1 can be used but such ratios may result in increased formation oflower functionality half-esters.

[0207] Useful anhydrides include aliphatic, cycloaliphatic, olefinic,cycloolefinic and aromatic anhydrides. Substituted aliphatic andaromatic anhydrides also are useful provided the substituents do notadversely affect the reactivity of the anhydride or the properties ofthe resultant polyester. Examples of substituents include chloro, alkyland alkoxy. Examples of anhydrides include succinic anhydride,methylsuccinic anhydride, dodecenyl succinic anhydride,octadecenylsuccinic anhydride, phthalic anhydride, tetrahydrophthalic anhyd ride, methyltetrahydrophthalic an hydride, hexahydrophthalic anhydride, alkyl hexahydrophthalic anhydrides such asmethylhexahydrophthalic anhydride (preferred), tetrachlorophthalicanhydride, endomethylene tetrahydrophthalic anhydride, chlorendicanhydride, itaconic anhydride, citraconic anhydride and maleicanhydride.

[0208] Among the polyols which can be used are simple polyols, that is,those containing from 2 to 20 carbon atoms, as well as polymeric polyolssuch as polyester polyols, polyurethane polyols and acrylic polyols.

[0209] Among the simple polyols which can be used are diols, triols,tetrols and mixtures thereof. Non-limiting examples of the polyolsinclude those containing from 2 to 10 carbon atoms such as aliphaticpolyols. Specific examples include but are not limited to the followingcompositions: di-trimethylol propane (bis(2,2-dimethylol)dibutylether);pentaerythritol; 1,2,3,4-butanetetrol; sorbitol; trimethylolpropane;trimethylolethane; 1,2,6-hexanetriol; glycerine; trishydroxyethylisocyanurate; dimethylol propionic acid; 1,2,4-butanetriol;2-ethyl-1,3-hexanediol; TMP/epsilon-caprolactone triols; ethyleneglycol; 1,2-propanediol; 1,3-propanediol; 1,4-butanediol;1,5-pentanediol: 1,6-hexanediol; neopentyl glycol; diethylene glycol;dipropylene glycol; 1,4-cyclohexanedimethanol and2,2,4-trimethylpentane-1,3 diol.

[0210] With regard to oligomeric polyols, suitable polyols which can beused are polyols made from reaction of diacids with triols, such astrimethylol propane/cyclohexane diacid and trimethylol propane/adipicacid.

[0211] With regard to polymeric polyols, the polyester polyols can beprepared by esterification of an organic polycarboxylic acid oranhydride thereof with organic polyols and/or an epoxide. Usually, thepolycarboxylic acids and polyols are aliphatic or aromatic dibasic acidsor acid anhydrides and diols.

[0212] The polyols which are usually employed in making the polyesterinclude trimethylol propane, di-trimethylol propane, alkylene glycolssuch as ethylene glycol, neopentyl glycol and other glycols such ashydrogenated bisphenol A, cyclohexanediol, cyclohexanedimethanol, thereaction products of lactones and diols, for example, the reactionproduct of epsilon-caprolactone and ethylene glycol, hydroxy-alkylatedbisphenols, polyester glycols for example poly(oxytetramethylene)glycol,and the like.

[0213] The acid component of the polyester comprises monomericcarboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule.Among the acids which can be used are phthalic acid, isophthalic acid,terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,methylhexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid,maleic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acidand other dicarboxylic acids of varying types. Also, there may beemployed higher polycarboxylic acids such as trimellitic acid andtricarballylic acid.

[0214] Besides the polyester polyols formed from polybasic acids andpolyols, polylactone-type polyesters also can be employed. Theseproducts can be formed from the reaction of a lactone such asepsilon-caprolactone and a polyol such as ethylene glycol, diethyleneglycol and trimethylolpropane.

[0215] Besides polyester polyols, polyurethane polyols such aspolyester-urethane polyols which can be formed from reacting an organicpolyisocyanate with a polyester polyol such as those described above canbe used. The organic polyisocyanate can be reacted with a polyol so thatthe OH/NCO equivalent ratio is greater than 1:1 so that the resultantproduct contains free hydroxyl groups. The organic polyisocyanate whichcan be used in preparing the polyurethane polyols can be an aliphatic oraromatic polyisocyanate or a mixture. Diisocyanates are preferred,although higher polyisocyanates such as triisocyanates can be used, butthey do result in higher viscosities.

[0216] Examples of suitable diisocyanates include 4,4′-diphenylmethanediisocyanate, 1,4-tetramethylene diisocyanate, isophorone diisocyanateand 4,4′-methylenebis(cyclohexyl isocyanate). Examples of suitablehigher functionality polyisocyanates include polymethylene polyphenolisocyanates.

[0217] At least a portion, and in certain instances all of the acidfunctional groups can be silylated. Alternatively at least a portion,and in certain instances all of the acid functional groups can beconverted to hydroxyl groups by reaction with an epoxide such as arediscussed above or aliphatic diol and then silylated.

[0218] Useful epoxy functional materials include epoxy functionalmonomers such as glycidyl methacrylate, ethylene oxide, butylene oxide,propylene oxide, cyclohexene oxide, glycidyl ethers such as phenylglycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether, isopropylglycidyl ether, glycidyl esters such as glycidyl versatate, for exampleCARDURA E available from Shell Chemical Co., and mixtures of any of theforegoing. Other useful epoxy functional materials include polymerscomprising at least two epoxide or oxirane groups per molecule. Thesematerials often are referred to as di- or polyepoxides.

[0219] The equivalent ratio of epoxy groups to acid groups on the estergenerally ranges from 0.1:1 to 2:1, can range from 0.5:1 to 1:1, andtypically ranges from 0.8:1 to 1:1, inclusive of these values.

[0220] Useful aliphatic diols include diols containing a primaryhydroxyl such as 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,2-hexanediol.1,5-hexanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropyleneglycol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, and3,3-dimethyl-1,2-butanediol.

[0221] In one embodiment, the present invention is directed to coatingcompositions as previously described, wherein the at least one materialcomprises at least one compound having the following structure (X):

[0222] Other useful materials having a linkage selected from an esterlinkage, a urethane linkage, a urea linkage, an amide linkage, asiloxane linkage, and an ether linkage and at least one reactivefunctional group which are suitable for silylation are disclosed abovein the discussion of suitable additional polymers.

[0223] Alternatively, useful reactants include acrylic polymerscontaining hydroxyl groups blocked with hydrolyzable siloxy groups(polymerized for example from vinyl monomers and trimethyl siloxymethylmethacrylate) such as are disclosed in I. Azuma et al., “AcrylicOligomer for High Solid Automotive Top Coating System Having ExcellentAcid Resistance”, Progress in Organic Coatings 32 (1997) 1-7, which isincorporated herein by reference.

[0224] In one embodiment, the present invention is directed tocompositions as previously described wherein the silyl-blocked reactant,when added to the other components which form the coating composition,is present in the composition in an amount ranging from 0.1 to 90 weightpercent based on total weight of the resin solids of the componentswhich form the coating composition. In another embodiment, the presentinvention is directed to compositions as previously described whereinthe silyl-blocked reactant, when added to the other components whichform the coating composition, is present in the coating composition inan amount of at least 0.1 weight percent based on total weight of theresin solids of the components which form the coating composition. Inanother embodiment, the present invention is directed to compositions aspreviously described wherein the silyl-blocked reactant, when added tothe other components which form the coating composition, is present inthe coating composition in an amount of at least 1 weight percent basedon total weight of the resin solids of the components which form thecoating composition. In another embodiment, the present invention isdirected to compositions as previously described wherein thesilyl-blocked reactant, when added to the other components which formthe coating composition in an amount of at least 5 weight percent basedon total weight of the resin solids of the components which form thecoating composition.

[0225] In yet another embodiment, the present invention is directed tocompositions as previously described wherein the silyl-blocked reactant,when added to the other components which form the coating composition,is present in the coating composition in an amount less than 60 weightpercent based on total weight of the resin solids of the componentswhich form the coating composition. In a further embodiment, the presentinvention is directed to compositions as previously described whereinthe silyl-blocked reactant, when added to the other components whichform the coating composition, is present in the coating composition inan amount less than 30 weight percent based on total weight of the resinsolids of the components which form the coating composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the silyl-biocked reactant, when added tothe other components which form the coating composition, is present inthe coating composition in an amount less than 10 weight percent basedon total weight of the resin solids of the components which form thecoating composition. The amount of the silyl-blocked reactant may rangebetween any combination of these values inclusive of the recited values.

[0226] In a further embodiment, the present invention is directed tocompositions as previously described wherein at least one film formingmaterial, different from at least one polysiloxane (a), is presentduring formation of the composition. This film forming material can be apolymer, in addition to the at least one polysiloxane (a), having atleast one functional group reactive with at least one functional groupof the at least one polysiloxane (a), and the at least one curing agent,if present. In one embodiment, this at least one additional polymer canhave at least one reactive functional group selected from a hydroxylgroup, a carbamate group, an epoxy group, an isocyanate group, and acarboxyl group. In another embodiment, the additional polymer can haveat least one reactive functional group selected from a hydroxyl group,and a carbamate group.

[0227] The additional polymer may contain one or more reactivefunctional groups selected from hydroxyl groups, carbamate groups, epoxygroups, isocyanate groups, carboxylic acid groups, and mixtures of anyof the foregoing.

[0228] Nonlimiting examples of suitable hydroxyl group-containingadditional polymers include acrylic polyols, polyester polyols,polyurethane polyols, polyether polyols, and mixtures of any of theforegoing. The additional polymer can be an acrylic polyol that can havea hydroxyl equivalent weight ranging from 1000 to 100 grams per solidequivalent.

[0229] Suitable hydroxyl group or carboxyl group-containing acrylicpolymers can be prepared from polymerizable ethylenically unsaturatedmonomers and can be copolymers of (meth)acrylic acid or hydroxylalkylesters of (meth)acrylic acid with one or more other polymerizableethylenically unsaturated monomers such as alkyl esters of (meth)acrylicacid including methyl (meth)acrylate, ethyl (meth)acrylate, butyl(meth)acrylate and 2-ethyl hexylacrylate, and vinyl aromatic compoundssuch as styrene, alpha-methyl styrene, and vinyl toluene. As usedherein, “(meth)acrylate” and like terms are intended to include bothacrylates and methacrylates.

[0230] The acrylic polymer can be prepared from ethylenicallyunsaturated, beta-hydroxy ester functional monomers. Such monomers canbe derived from the reaction of an ethylenically unsaturated acidfunctional monomer, such as monocarboxylic acids, for example, acrylicacid, and an epoxy compound which does not participate in the freeradical initiated polymerization with the unsaturated acid monomer.Nonlimiting examples of such epoxy compounds are glycidyl ethers andesters. Nonlimiting examples of suitable glycidyl ethers compriseglycidyl ethers of alcohols and phenols such as butyl glycidyl ether,octyl glycidyl ether, phenyl glycidyl ether, and the like. Nonlimitingexamples of suitable glycidyl esters include those which arecommercially available from Shell Chemical Company under the tradenameCARDURA E and from Exxon Chemical Company under the tradenameGLYDEXX-10. Alternatively, the beta-hydroxy ester functional monomersare prepared from an ethylenically unsaturated, epoxy functionalmonomer, for example glycidyl (meth)acrylate and allyl glycidyl ether,and a saturated carboxylic acid such as a saturated monocarboxylic acid,for example isostearic acid.

[0231] Epoxy functional groups can be incorporated into the polymerprepared from polymerizable ethylenically unsaturated monomers bycopolymerizing oxirane group-containing monomers, for example glycidyl(meth)acrylate and allyl glycidyl ether, with other polymerizableethylenically unsaturated monomers, such as those discussed above.Preparation of such epoxy functional acrylic polymers is described indetail in U.S. Pat. No. 4,001,156 at columns 3 to 6, which columns arespecifically incorporated herein by reference.

[0232] Carbamate functional groups can be incorporated into the polymerprepared from polymerizable ethylenically unsaturated monomers bycopolymerizing, for example, the above-described ethylenicallyunsaturated monomers with a carbamate functional vinyl monomer such as acarbamate functional alkyl ester of methacrylic acid. Useful carbamatefunctional alkyl esters can be prepared by reacting, for example, ahydroxyalkyl carbamate (which can be the reaction product of ammonia andethylene carbonate or propylene carbonate) with methacrylic anhydride.

[0233] Other useful carbamate functional vinyl monomers include, forinstance, the reaction product of hydroxyethyl methacrylate, isophoronediisocyanate, and hydroxypropyl carbamate; or the reaction product ofhydroxypropyl methacrylate, isophorone diisocyanate, and methanol. Stillother carbamate functional vinyl monomers may be used, such as thereaction product of isocyanic acid (HNCO) with a hydroxyl functionalacrylic or methacrylic monomer such as hydroxyethyl acrylate, and thosemonomers described in U.S. Pat. No. 3,479,328, which is incorporatedherein by reference. Carbamate functional groups also can beincorporated into the acrylic polymer by reacting a hydroxyl functionalacrylic polymer with a low molecular weight alkyl carbamate such asmethyl carbamate. Pendant carbamate groups also can be incorporated intothe acrylic polymer by a “transcarbamoylation” reaction in which ahydroxyl functional acrylic polymer is reacted with a low molecularweight carbamate derived from an alcohol or a glycol ether. Thecarbamate groups can exchange with the hydroxyl groups to yield thecarbamate functional acrylic polymer and the original alcohol or glycolether. Also, hydroxyl functional acrylic polymers can be reacted withisocyanic acid to provide pendent carbamate groups. Likewise, hydroxylfunctional acrylic polymers can be reacted with urea to provide pendentcarbamate groups.

[0234] The polymers prepared from polymerizable ethylenicallyunsaturated monomers can be prepared by solution polymerizationtechniques, which are well-known to those skilled in the art, in thepresence of suitable catalysts such as organic peroxides or azocompounds, for example benzoyl peroxide orN,N-azobis(isobutylronitrile). The polymerization can be carried out inan organic solution in which the monomers are soluble by techniquesconventional in the art. Alternatively, these polymers can be preparedby aqueous emulsion or dispersion polymerization techniques which arewell-known in the art. The ratio of reactants and reaction conditionsare selected to result in an acrylic polymer with the desired pendentfunctionality.

[0235] Polyester polymers also are useful in the compositions of theinvention as the additional polymer. Useful polyester polymers cancomprise the condensation products of polyhydric alcohols andpolycarboxylic acids. Nonlimiting examples of suitable polyhydricalcohols include ethylene glycol, neopentyl glycol, trimethylol propane,and pentaerythritol. Nonlimiting examples of suitable polycarboxylicacids include adipic acid, 1,4-cyclohexyl dicarboxylic acid, andhexahydrophthalic acid. Besides the polycarboxylic acids mentionedabove, functional equivalents of the acids such as anhydrides where theyexist or lower alkyl esters of the acids such as the methyl esters canbe used. Also, small amounts of monocarboxylic acids such as stearicacid can be used. The ratio of reactants and reaction conditions areselected to result in a polyester polymer with the desired pendentfunctionality, i.e., carboxyl or hydroxyl functionality.

[0236] For example, hydroxyl group-containing polyesters can be preparedby reacting an anhydride of a dicarboxylic acid such ashexahydrophthalic anhydride with a diol such as neopentyl glycol in a1:2 molar ratio. Where it is desired to enhance air-drying, suitabledrying oil fatty acids may be used and can include those derived fromlinseed oil, soya bean oil, tall oil, dehydrated castor oil, or tungoil.

[0237] Carbamate functional polyesters can be prepared by first forminga hydroxyalkyl carbamate that can be reacted with the polyacids andpolyols used in forming the polyester. Alternatively, terminal carbamatefunctional groups can be incorporated into the polyester by reactingisocyanic acid with a hydroxy functional polyester. Also, carbamatefunctionality can be incorporated into the polyester by reacting ahydroxyl polyester with a urea. Additionally, carbamate groups can beincorporated into the polyester by a transcarbamoylation reaction.Preparation of suitable carbamate functional group-containing polyestersare those described in U.S. Pat. No. 5,593,733 at column 2, line 40 tocolumn 4, line 9, which is incorporated herein by reference.

[0238] Polyurethane polymers containing terminal isocyanate or hydroxylgroups also can be used as the additional polymer in the compositions ofthe invention. The polyurethane polyols or NCO-terminated polyurethaneswhich can be used are those prepared by reacting polyols includingpolymeric polyols with polyisocyanates. Polyureas containing terminalisocyanate or primary or secondary amine groups which also can be usedcan be those prepared by reacting polyamines including, but not limitedto, polymeric polyamines with polyisocyanates.

[0239] The hydroxyl/isocyanate or amine/isocyanate equivalent ratio canbe adjusted and reaction conditions can be selected to obtain thedesired terminal groups. Nonlimiting examples of suitablepolyisocyanates include those described in U.S. Pat. No. 4,046,729 atcolumn 5, line 26 to column 6, line 28, which portion is incorporatedherein by reference. Nonlimiting examples of suitable polyols includethose described in U.S. Pat. No. 4,046,729 at column 7, line 52 tocolumn 10, line 35, which portion is incorporated herein by reference.Nonlimiting examples of suitable polyamines include those described inU.S. Pat. No. 4,046,729 at column 6, line 61 to column 7, line 32 and inU.S. Pat. No. 3,799,854 at column 3, lines 13 to 50, the indicatedportions of both are incorporated herein by reference.

[0240] Carbamate functional groups can be introduced into thepolyurethane polymers by reacting a polyisocyanate with a polyesterhaving hydroxyl functionality and containing pendent carbamate groups.Alternatively, the polyurethane can be prepared by reacting apolyisocyanate with a polyester polyol and a hydroxyalkyl carbamate orisocyanic acid as separate reactants. Nonlimiting examples of suitablepolyisocyanates include aromatic isocyanates (such as4,4′-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate andtoluene diisocyanate) and aliphatic polyisocyanates (such as1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate).Cycloaliphatic diisocyanates, such as 1,4-cyclohexyl diisocyanate andisophorone diisocyanate can be employed.

[0241] Nonlimiting examples of suitable polyether polyols includepolyalkylene ether polyols such as those having the following structuralformulas (VII) or (VIII):

[0242] wherein the substituent group R represents hydrogen or a loweralkyl group of 1 to 5 carbon atoms including mixed substituents, n has avalue ranging from 2 to 6, and m has a value ranging from 8 to 100 orhigher. Nonlimiting examples of polyalkylene ether polyols includepoly(oxytetramethylene) glycols, poly(oxytetraethylene) glycols,poly(oxy-1,2-propylene) glycols, and poly(oxy-1,2-butylene) glycols.

[0243] Also useful can be polyether polyols formed from oxyalkylation ofvarious polyols, for example, but not limited to, glycols such asethylene glycol, 1,6-hexanediol, Bisphenol A, and the like, or otherhigher polyols such as trimethylolpropane, pentaerythritol, and thelike. Polyols of higher functionality which can be utilized as indicatedcan be made, for instance, by oxyalkylation of compounds such as sucroseor sorbitol. One oxyalkylation method that can be used is reaction of apolyol with an alkylene oxide, including but not limited to, propyleneor ethylene oxide, in the presence of an acidic or basic catalyst.Specific, nonlimiting examples of polyethers include those sold underthe names TERATHANE and TERACOL, available from E. I. duPont de Nemoursand Co., Inc.

[0244] In one embodiment, the present invention is directed to a curedcomposition as previously described in which the at least onefilm-forming material comprises reactive functional groups which arethermally curable functional groups. In an alternative embodiment, atleast one of the reactive functional groups of the film-forming materialcan be curable by ionizing radiation or actinic radiation. In anotheralternative embodiment, the film-forming material can comprise at leastone functional group which is curable by thermal energy and at least onefunctional group which is curable by ionizing or actinic radiation.

[0245] Useful radiation-curable groups which can be present as reactivefunctional groups on the polysiloxane include unsaturated groups such asvinyl groups, vinyl ether groups, epoxy groups, maleimide groups,fumarate groups and combinations of the foregoing. In one embodiment,the UV curable groups can include acrylate groups, maleimides,fumarates, and vinyl ethers. Suitable vinyl groups include those havingunsaturated ester groups and vinyl ether groups as discussed below.

[0246] In one embodiment, the at least one additional polymer can have aweight average molecular weight (Mw) ranging from 1000 to 20,000, asdetermined by gel permeation chromatography using a polystyrenestandard. In another embodiment, the Mw of the at least one additionalpolymer ranges from 1500 to 15,000, and can range from 2000 to 12,000,as determined by gel permeation chromatography using a polystyrenestandard.

[0247] It should be mentioned that in embodiments where at least one ofeach of the at least one polysiloxane (a) and the at least oneadditional polymer are present during the formation of the composition,the reactive functional groups of the at least one polysiloxane (a) andthe additional polymer can be the same or different, but each must bereactive with at least functional group of the curing agent if employed.Nonlimiting examples of such reactive functional groups include hydroxylgroups, carboxylic acid groups, isocyanate groups, carboxylate groups,primary amine groups, secondary amine groups, amide groups, carbamategroups, and epoxy groups.

[0248] In an embodiment of the present invention, the additional polymerhaving at least one reactive functional group, if employed, is generallypresent, when added to the other components in the composition, in anamount of at least 2 percent by weight. That additional polymer can bepresent in an amount of at least 5 percent by weight, and is typicallypresent in an amount of at least 10 percent by weight based on totalweight of the resin solids of the components which form the composition.Also the additional polymer having at least one reactive functionalgroup, if employed, is generally present, when added to the othercomponents in the composition, in an amount of less than 80 percent byweight. It can be present in an amount of less than 60 percent byweight, and is typically present in an amount of less than 50 percent byweight based on total weight of the resin solids of the components whichform the composition. The amount of the additional polymer having atleast one reactive functional groups present in the compositions mayrange between any combination of these values inclusive of the recitedvalues.

[0249] The compositions of the present invention can be solvent-basedcompositions, water-based compositions, in solid particulate form, thatis, a powder composition, or in the form of a powder slurry or aqueousdispersion. The components of the present invention used to form thecured compositions of the present invention can be dissolved ordispersed in an organic solvent. Nonlimiting examples of suitableorganic solvents include alcohols, such as butanol; ketones, such asmethyl amyl ketone; aromatic hydrocarbons, such as xylene; and glycolethers, such as, ethylene glycol monobutyl ether; esters; othersolvents; and mixtures of any of the foregoing.

[0250] In solvent based compositions, the organic solvent is generallypresent in amounts ranging from 5 to 80 percent by weight based on totalweight of the resin solids of the components which form the composition,and can be present in an amount ranging from 30 to 50 percent by weight,inclusive of the recited values. The compositions as described above canhave a total solids content ranging from 40 to 75 percent by weightbased on total weight of the resin solids of the components which formthe composition, and can have a total solids content ranging from 50 to70 percent by weight, inclusive of the recited values. Alternatively,the inventive compositions can be in solid particulate form suitable foruse as a powder coating, or suitable for dispersion in a liquid mediumsuch as water for use as a powder slurry.

[0251] In a further embodiment where the compositions as previouslydescribed are formed from at least one reactant, a catalyst isadditionally present during the composition's formation. In oneembodiment, the catalyst is present in an amount sufficient toaccelerate the reaction between at least one reactive functional groupof the reactant and at least one reactive functional group of the atleast one polysiloxane (a). In one embodiment, the catalyst is an acidcatalyst.

[0252] Nonlimiting examples of suitable catalysts include acidicmaterials, for example, acid phosphates, such as phenyl acid phosphate,and substituted or unsubstituted sulfonic acids such as dodecylbenzenesulfonic acid or para-toluene sulfonic acid. Non-limiting examples ofsuitable catalysts for reactions between isocyanate groups and hydroxylgroups include tin catalysts such as dibutyl tin dilaurate. Non-limitingexamples of epoxy acid base catalysts include tertiary amines such asN,N′-dimethyldodecyl amine. In another embodiment, the catalyst can be aphosphatized polyester or a phosphatized epoxy. In this embodiment, thecatalyst can be, for example, the reaction product of phosphoric acidand a bisphenol A diglycidyl ether having two hydrogenated phenolicrings, such as DRH-151, which is commercially available from ShellChemical Co. The catalyst can be present, when added to the othercomponents of the composition, in an amount ranging from 0.1 to 5.0percent by weight, and is typically present in an amount ranging from0.5 to 1.5 percent by weight based on the total weight of thecomposition, inclusive of the recited values.

[0253] In another embodiment, additional components can be presentduring the formation of the compositions as previously described. Theseadditional components include, but are not limited to, flexibilizers,plasticizers, surface active agents as defined herein (such aspolysiloxanes), thixotropic agents, anti-gassing agents, organiccosolvents, flow controllers, hindered amine light stabilizers,anti-oxidants, UV light absorbers, coloring agents or tints, and similaradditives conventional in the art, as well as mixtures of any of theforegoing can be included in the composition. These additionalingredients can present, when added to the other components of thecomposition, in an amount up to 40 percent by weight based on the totalweight of the resin solids of the components which form the composition.

[0254] In yet another embodiment of the present invention, at least onesurface active agent can be present during the formation of thecompositions as previously described. The at least one surface activeagent can be selected from anionic, nonionic, and cationic surfaceactive agents.

[0255] As used herein, by “surface active agent” is meant any materialwhich tends to lower the solid surface tension or surface energy of thecured composition or coating. That is, the cured composition or coatingformed from a composition formed from components comprising a surfaceactive agent has a lower solid surface tension or surface energy than acured coating formed from the analogous composition which does notcontain the surface active agent during its formation.

[0256] For purposes of the present invention, solid surface tension canbe measured according to the Owens-Wendt method using a Rame'-HartContact Angle Goniometer with distilled water and methylene iodide asreagents. Generally, a 0.02 cc drop of one reagent is placed upon thecured coating surface and the contact angle and its complement aremeasured using a standard microscope equipped with the goniometer. Thecontact angle and its complement are measured for each of three drops.The process is then repeated using the other reagent. An average valueis calculated for the six measurements for each of the reagents. Thesolid surface tension is then calculated using the Owens-Wendt equation:

{γ|(1+cos Φ)}/2=(γ|^(d)γ_(s) ^(d))^(1/2)+(γ|^(F)γ_(s) ^(p))^(1/2)

[0257] where γ| is the surface tension of the liquid (methyleneiodide=50.8, distilled water=72.8) and γ^(d) and γ^(p) are thedispersion and polar components (methylene iodide γ^(d)=49.5, γ^(p)=1.3;distilled water γ^(d)=21.8, γ^(p)=51.0); the values for Φ measured andthe cos Φ determined. Two equations are then setup, one for methyleneiodide and one for water. The only unknowns are γ_(s) ^(d) and γ_(s)^(p). The two equations are then solved for the two unknowns. The twocomponents combined represent the total solid surface tension.

[0258] The at least one surface active agent can be selected fromamphiphilic, reactive functional group-containing polysiloxanes,amphiphilic fluoropolymers, and mixtures of any of the foregoing. Withreference to water-soluble or water-dispersible amphiphilic materials,the term “amphiphilic” means a polymer having a generally hydrophilicpolar end and a water-insoluble generally hydrophobic end. Nonlimitingexamples of suitable functional group-containing polysiloxanes for useas surface active agents include the at least one polysiloxanesdescribed above. Nonlimiting examples of suitable amphiphilicfluoropolymers include fluoroethylene-alkyl vinyl ether alternatingcopolymers (such as those described in U.S. Pat. No. 4,345,057)available from Asahi Glass Company under the tradename LUMIFLON;fluorosurfactants, such as the fluoroaliphatic polymeric esterscommercially available from 3M of St. Paul, Minn. under the tradenameFLUORAD; functionalized perfluorinated materials, such as1H,1H-perfluoro-nonanol commercially available from FluoroChem USA; andperfluorinated (meth)acrylate resins.

[0259] Nonlimiting examples of other surface active agents suitable foruse in the cured composition or coating of the present invention caninclude anionic, nonionic and cationic surface active agents.

[0260] Nonlimiting examples of suitable anionic surface active agentsinclude sulfates or sulfonates. Specific nonlimiting examples includehigher alkyl mononuclear aromatic sulfonates such as the higher alkylbenzene sulfonates containing from 10 to 16 carbon atoms in the alkylgroup and a straight- or branched-chain, e.g., the sodium salts ofdecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecylbenzene sulfonate and the higher alkyl toluene, xylene and phenolsulfonates; alkyl naphthalene sulfonate, and sodium dinonyl naphthalenesulfonate. Other nonlimiting examples of suitable anionic surface activeagents include olefin sulfonates, including long chain alkenylenesulfonates, long chain hydroxyalkane sulfonates, and mixtures of any ofthe foregoing. Nonlimiting examples of other sulfate or sulfonatedetergents are paraffin sulfonates such as the reaction products ofalpha olefins and bisulfites (e.g., sodium bisulfite). Also comprisedare sulfates of higher alcohols, such as sodium lauryl sulfate, sodiumtallow alcohol sulfate, or sulfates of mono-or di-glycerides of fattyacids (e.g., stearic monoglyceride monosulfate), alkyl poly(ethoxy)ethersulfates including, but not limited to, the sulfates of the condensationproducts of ethylene oxide and lauryl alcohol (usually having 1-5ethenoxy groups per molecule); lauryl or other higher alkyl glycerylether sulfonates; aromatic poly(ethenoxy)ether sulfates including, butnot limited to, the sulfates of the condensation products of ethyleneoxide and nonyl phenol (usually having 1-20 oxyethylene groups permolecule).

[0261] Further nonlimiting examples include salts of sulfated aliphaticalcohol, alkyl ether sulfate or alkyl aryl ethoxy sulfate available fromRhone-Poulenc under the general tradename ABEX. Phosphate mono-ordi-ester type anionic surface active agents also can be used. Theseanionic surface active agents are well known in the art and arecommercially available under the general trademark GAFAC from GAFCorporation and under the general trademark TRITON from Rohm & HaasCompany.

[0262] Nonlimiting examples of nonionic surface active agents suitablefor use in the cured composition or coating of the present inventioninclude those containing ether linkages and which are represented by thefollowing general formula: RO(R′O)_(n)H; wherein the substituent group Rrepresents a hydrocarbon group containing 6 to 60 carbon atoms, thesubstituent group R′ represents an alkylene group containing 2 or 3carbon atoms, and mixtures of any of the foregoing, and n is an integerranging from 2 to 100.

[0263] Such nonionic surface active agents can be prepared by treatingfatty alcohols or alkyl-substituted phenols with an excess of ethyleneor propylene oxide. The alkyl carbon chain may contain from 14 to 40carbon atoms and may be derived from a long chain fatty alcohol such asoleyl alcohol or stearyl alcohol. Nonionic polyoxyethylene surfaceactive agents of the type represented by the formula above arecommercially available under the general trade designation SURFYNOL fromAir Products Chemicals, Inc.; PLURONIC or TETRONIC from BASFCorporation; TERGITOL from Union Carbide; and SURFONIC from HuntsmanCorporation. Other nonlimiting examples of suitable nonionic surfaceactive agents include block copolymers of ethylene oxide and propyleneoxide based on a glycol such as ethylene glycol or propylene glycolincluding, but not limited to, those available from BASF Corporationunder the general trade designation PLURONIC.

[0264] As indicated above, cationic surface active agents also can beused. Nonlimiting examples of cationic surface active agents suitablefor use in the cured compositions or coatings of the present inventioninclude acid salts of alkyl amines such as ARMAC HT, an acetic acid saltof n-alkyl amine available from Akzo Nobel Chemicals; imidazolinederivatives such as CALGENE C-100 available from Calgene Chemicals Inc.;ethoxylated amines or amides such as DETHOX Amine C-5, a cocoamineethoxylate available from Deforest Enterprises; ethoxylated fatty aminessuch as ETHOX TAM available from Ethox Chemicals, Inc.; and glycerylesters such as LEXEMUL AR, a glyceryl stearate/stearaidoethyldiethylamine available from Inolex Chemical Co.

[0265] Other examples of suitable surface active agents can includepolyacrylates. Nonlimiting examples of suitable polyacrylates includehomopolymers and copolymers of acrylate monomers, for examplepolybutylacrylate and copolymers derived from acrylate monomers (such asethyl (meth)acrylate, 2-ethylhexylacrylate, butyl (meth)acrylate andisobutyl acrylate), and hydroxy ethyl(meth)acrylate and (meth)acrylicacid monomers. In one embodiment, the polyacrylate can have amino andhydroxy functionality. Suitable amino and hydroxyl functional acrylatesare disclosed in Example 26 below and in U.S. Pat. No. 6,013,733, whichis incorporated herein by reference. Another example of a useful aminoand hydroxyl functional copolymer is a copolymer of hydroxy ethylacrylate, 2-ethylhexylacrylate, isobutyl acrylate and dimethylaminoethylmethacrylate. In another embodiment, the polyacrylate can have acidfunctionality, which can be provided, for example, by including acidfunctional monomers such as (meth)acrylic acid in the components used toprepare the polyacrylate. In another embodiment, the polyacrylate canhave acid functionality and hydroxyl functionality, which can beprovided, for example, by including acid functional monomers such as(meth)acrylic acid and hydroxyl functional monomers such as hydroxyethyl (meth)acrylate in the components used to prepare the polyacrylate.

[0266] In one embodiment, the present invention is directed to a powdercomposition formed from components comprising:

[0267] (a) at least one surface active agent comprising:

[0268] (i) at least one polysiloxane comprising at least one reactivefunctional group, the at least one polysiloxane comprising at least oneof the following structural units (I):

R¹ _(n)R² _(m)SiO₍₄₋ n-m)/2  (I)

[0269] wherein each R¹, which may be identical or different, representsH, OH, a monovalent hydrocarbon group or a monovalent siloxane group;each R², which may be identical or different, represents a groupcomprising at least one reactive functional group, wherein m and nfulfill the requirements of 0<n<4, 0<m<4 and 2≦(m+n)<4; and

[0270] (ii) at least one polyacrylate surface active agent having atleast one functional group selected from amino and hydroxylfunctionality, acid functionality and acid and hydroxyl functionality;and

[0271] (b) a plurality of particles,

[0272] wherein each component is different, and

[0273] wherein the at least one reactive functional group of the atleast one polysiloxane and the at least one functional group of the atleast one polyacrylate surface active agent are substantiallynonreactive with the particles.

[0274] In yet another embodiment, the present invention is directed to acoated substrate comprising a substrate and a composition coated over atleast a portion of the substrate, wherein the composition is selectedfrom any of the foregoing compositions. In still another embodiment, thepresent invention is directed to a method of coating a substrate whichcomprises applying a composition over at least a portion of thesubstrate, wherein the composition is selected from any of the foregoingcompositions. In another embodiment, the present invention is directedto a method for forming a cured coating on a substrate comprisingapplying over at least a portion of the substrate a coating compositionaccording to any of the foregoing compositions.

[0275] In another embodiment, the present invention is directed to amethod of coating a substrate further comprising a step of curing thecomposition after application to the substrate. The components used toform the compositions in these embodiments can be selected from thecomponents discussed above.

[0276] As used herein, a composition “over at least a portion of asubstrate” refers to a composition directly applied to at least aportion of the substrate, as well as a composition applied to anycoating material which was previously applied to at least a portion ofthe substrate.

[0277] The compositions of the present invention can be applied overvirtually any substrate including wood, metals, glass, cloth, plastic,foam, polymeric substrates such as elastomeric substrates and the like.In one embodiment, the present invention is directed to a coatedsubstrate as previously described wherein the coated substrate is aflexible substrate. In another embodiment, the present invention isdirected to a coated substrate as previously described wherein thecoated substrate is a rigid substrate.

[0278] In a further embodiment, the present invention is directed tocoated substrates as previously described wherein the coated substrateis a ceramic substrate. In still another embodiment, the presentinvention is directed to coated substrates as previously describedwherein the coated substrate is a polymeric substrate. In anotherembodiment, the present invention is directed to a coated metallicsubstrate comprising a metallic substrate and a composition coated overat least a portion of the metallic substrate, wherein the composition isselected from any of the foregoing compositions. The components used toform the compositions in these embodiments can be selected from thecomponents discussed above, and additional components also can beselected from those recited above.

[0279] A further embodiment of the present invention is directed to acoated automobile substrate comprising an automobile substrate and acomposition coated over at least a portion of the automobile substrate,wherein the composition is selected from any of the foregoingcompositions. In yet another embodiment, the present invention isdirected to a method of making a coated automobile substrate comprisingproviding an automobile substrate and applying over at least a portionof the automotive substrate a composition selected from any of theforegoing compositions. Again, the components used to form thecompositions in these embodiments can be selected from the componentsdiscussed above, and additional components also can be selected fromthose recited above.

[0280] Suitable flexible elastomeric substrates can include any of thethermoplastic or thermoset synthetic materials well known in the art.Nonlimiting examples of suitable flexible elastomeric substratematerials include polyethylene, polypropylene, thermoplastic polyolefin(“TPO”), reaction injected molded polyurethane (“RIM”), andthermoplastic polyurethane (“TPU”).

[0281] Nonlimiting examples of thermoset materials useful as substratesin connection with the present invention include polyesters, epoxides,phenolics, polyurethanes such as “RIM” thermoset materials, and mixturesof any of the foregoing. Nonlimiting examples of suitable thermoplasticmaterials include thermoplastic polyolefins such as polyethylene,polypropylene, polyamides such as nylon, thermoplastic polyurethanes,thermoplastic polyesters, acrylic polymers, vinyl polymers,polycarbonates, acrylonitrile-butadiene-styrene (“ABS”) copolymers,ethylene propylene diene terpolymer (“EPDM”) rubber, copolymers, andmixtures of any of the foregoing.

[0282] Nonlimiting examples of suitable metal substrates include ferrousmetals (e.g., iron, steel, and alloys thereof), nonferrous metals (e.g.,aluminum, zinc, magnesium, and alloys thereof), and mixtures of any ofthe foregoing. In the particular use of automobile components, thesubstrate can be formed from cold rolled steel, electrogalvanized steelsuch as hot dip electrogalvanized steel, electrogalvanized iron-zincsteel, aluminum, and magnesium.

[0283] When the substrates are used as components to fabricateautomotive vehicles (including, but not limited to, automobiles, trucksand tractors) they can have any shape, and can be selected from themetallic and flexible substrates described above. Typical shapes ofautomotive body components can include bodies (frames), hoods, doors,mirror housings, fenders, bumpers, and trim for automotive vehicles.

[0284] In a further embodiment, the present invention is directed tocoated automotive substrates as previously described wherein the coatedautomotive substrate is a hood. In another embodiment, the presentinvention is directed to coated automotive substrates as previouslydescribed wherein the coated automotive substrate is a door. In anotherembodiment, the present invention is directed to coated automotivesubstrates as previously described wherein the coated automotivesubstrate is a fender. In another embodiment, the present invention isdirected to coated automotive substrates as previously described whereinthe coated automotive substrate is a mirror housing. In anotherembodiment, the present invention is directed to coated automotivesubstrates as previously described wherein the coated automotivesubstrate is a quarterpanel. The components used to form thecompositions used to coat the automotive substrates in these embodimentscan be selected from the components discussed above, and additionalcomponents also can be selected from those recited above.

[0285] In embodiments of the present invention directed to automotiveapplications, the cured compositions can be, for example, theelectrodeposition coating, the primer coating, the basecoat, and/or thetopcoat. Suitable topcoats include monocoats and basecoat/clearcoatcomposites. Monocoats are formed from one or more layers of a coloredcoating composition. Basecoat/clearcoat composites comprise one or morelayers of a colored basecoat composition, and one or more layers of aclearcoating composition, wherein the basecoat composition has at leastone component which is different from the clearcoat composition. In theembodiments of the present invention directed to automotiveapplications, the clearcoat can be transparent after application.

[0286] In another embodiment, the present invention is directed tomulti-component composite coating compositions comprising a basecoatdeposited from a pigmented coating composition, and a topcoatingcomposition applied over at least a portion of the basecoat, wherein thetopcoating composition is selected from any of the compositionspreviously described. In one embodiment, the present invention isdirected to a multi-component composite coating composition aspreviously described, wherein the topcoating composition is transparentafter curing and is selected from any of the compositions previouslydescribed. The components used to form the topcoating composition inthese embodiments can be selected from the coating components discussedabove.

[0287] The basecoat and transparent topcoat (i.e., clearcoat)compositions used in the multi-component composite coating compositionsof the present invention in certain instances can be formulated intoliquid high solids coating compositions, that is, compositions generallycontaining 40 percent, or in certain instances greater than 50 percentby weight resin solids. The solids content can be determined by heatinga sample of the composition to 105° C. to 110° C. for 1-2 hours to driveoff the volatile material, and subsequently measuring relative weightloss. As aforementioned, although the compositions can be liquid coatingcompositions, they also can be formulated as powder coatingcompositions.

[0288] The coating composition of the basecoat in the color-plus-clearsystem can be any of the compositions useful in coatings applications,particularly automotive applications. The coating composition of thebasecoat can comprise a resinous binder and a pigment to act as thecolorant. Nonlimiting examples of resinous binders are acrylic polymers,polyesters, alkyds, and polyurethanes.

[0289] The resinous binders for the basecoat can be organicsolvent-based materials such as those described in U.S. Pat. No.4,220,679, note column 2, line 24 continuing through column 4, line 40,which portions are incorporated by reference. Also, water-based coatingcompositions such as those described in U.S. Pat. Nos. 4,403,003,4,147,679 and 5,071,904 can be used as the binder in the basecoatcomposition. These U.S. patents are incorporated herein by reference.

[0290] The basecoat composition can comprise one or more pigments ascolorants. Nonlimiting examples of suitable metallic pigments includealuminum flake, copper bronze flake, and metal oxide coated mica.

[0291] Besides the metallic pigments, the basecoat compositions cancontain nonmetallic color pigments conventionally used in surfacecoatings such as inorganic pigments such as titanium dioxide, ironoxide, chromium oxide, lead chromate, and carbon black; and organicpigments such as phthalocyanine blue and phthalocyanine green.

[0292] Optional ingredients in the basecoat composition can comprisethose which are well known in the art of formulating surface coatingsand can comprise surface active agents, flow control agents, thixotropicagents, fillers, anti-gassing agents, organic co-solvents, catalysts,and other customary auxiliaries. Nonlimiting examples of these materialsand suitable amounts are described in U.S. Pat. Nos. 4,220,679;4,403,003; 4,147,769; and 5,071,904, which patents are incorporatedherein by reference.

[0293] The basecoat compositions can be applied to the substrate by anyconventional coating technique such as brushing, spraying, dipping, orflowing. Spray techniques and equipment for air spraying, airless spray,and electrostatic spraying in either manual or automatic methods, knownin the art can be used.

[0294] During application of the basecoat to the substrate, the filmthickness of the basecoat formed on the substrate can range from 0.1 to5 mils. In another embodiment, the film thickness of the basecoat formedon the substrate can range 0.1 to 1 mils, and can be 0.4 mils.

[0295] After forming a film of the basecoat on the substrate, thebasecoat can be cured or alternatively given a drying step in whichsolvent is driven out of the basecoat film by heating or an air dryingperiod before application of the clearcoat. Suitable drying conditionsmay depend on the particular basecoat composition, and on the ambienthumidity if the composition is water-bome, but a drying time from 1 to15 minutes at a temperature of 750 to 200° F. (21° to 93° C.) can beadequate.

[0296] The transparent or clear topcoat composition can be applied tothe basecoat by any conventional coating technique, including, but notlimited to, compressed air spraying, electrostatic spraying, and eithermanual or automatic methods. The transparent topcoat can be applied to acured or to a dried basecoat before the basecoat has been cured. In thelatter instance, the two coatings can then be heated to cure bothcoating layers simultaneously. Typical curing conditions can range from50° F. to 475° F. (10° C. to 246° C.) for 1 to 30 minutes.Alternatively, the transparent topcoat can be cured by ionizing oractinic radiation or the combination of thermal energy and ionizing oractinic radiation as described in detail above. The clearcoatingthickness (dry film thickness) can be 1 to 6 mils.

[0297] A second topcoat coating composition can be applied to the firsttopcoat to form a “clear-on-clear” topcoat. The first topcoat coatingcomposition can be applied over at least a portion of the basecoat asdescribed above. The second topcoat coating composition can be appliedto a cured or to a dried first topcoat before the basecoat and firsttopcoat have been cured. The basecoat, the first topcoat, and the secondtopcoat can then be heated to cure the three coatings simultaneously.

[0298] It should be understood that the second transparent topcoat andthe first transparent topcoat coating compositions can be the same ordifferent provided that, when applied wet-on-wet, one topcoat does notsubstantially interfere with the curing of the other for example byinhibiting solvent/water evaporation from a lower layer. Moreover, thefirst topcoat, the second topcoat or both can be the coating compositionof the present invention. The first transparent topcoat coatingcomposition can be virtually any transparent topcoating compositionknown to those skilled in the art. The first transparent topcoatcomposition can be water-borne or solventborne, or, alternatively, insolid particulate form, i.e., a powder coating.

[0299] Nonlimiting examples of suitable first topcoating compositionsinclude crosslinkable coating compositions comprising at least onethermoseftable coating material and at least one curing agent. Suitablewaterbome clearcoats are disclosed in U.S. Pat. No. 5,098,947, which isincorporated herein by reference, and are based on water-soluble acrylicresins. Useful solvent borne clearcoats are disclosed in U.S. Pat. Nos.5,196,485 and 5,814,410, which are incorporated herein by reference, andinclude polyepoxides and polyacid curing agents. Suitable powderclearcoats are described in U.S. Pat. No. 5,663,240, which patent isincorporated herein by reference, and include epoxy functional acryliccopolymers and polycarboxylic acid curing agents.

[0300] Typically, after forming the first topcoat over at least aportion of the basecoat, the first topcoat is given a drying step inwhich solvent is driven out of the film by heating or, alternatively, anair drying period or curing step, before the application of the secondtopcoat. Suitable drying conditions will depend on the particular firsttopcoat composition, and on the ambient humidity if the composition iswater-bome, but, in general, a drying time from 1 to 15 minutes at atemperature of 75° to 200° F. (21° C. to 93° C.) will be adequate.

[0301] The polysiloxane-containing second topcoat coating composition ofthe present invention can be applied as described above for the firsttopcoat by any conventional coating application technique. Curingconditions can be those described above for the topcoat. The secondtopcoating dry film thickness can range from 0.1 to 3 mils.

[0302] It should be mentioned that the polysiloxane-containing coatingcompositions can be advantageously formulated as a “monocoat,” that is,a coating which forms essentially one coating layer when applied to asubstrate. The monocoat coating composition can be pigmented.Nonlimiting examples of suitable pigments include those mentioned above.When employed as a monocoat, the polysiloxane-containing coatingcompositions of the present invention can be applied (by any of theconventional application techniques discussed above) in two or moresuccessive coats, and, in certain instances can be applied with only anambient flash period between coats. The multi-coats when cured can formessentially one coating layer.

[0303] In another embodiment, the present invention is directed to amethod for making a multi-component composite comprising (a) applying apigmented composition to a substrate to form a basecoat; and (b)applying a topcoating composition over at least a portion of thebasecoat to form a topcoat thereon, wherein the topcoating compositionis selected from any of the compositions described above. The topcoatcan be cured. The components used to form the topcoating composition inthis embodiment can be selected from the coating components discussedabove, and additional components also can be selected from those recitedabove. In another embodiment, the coating composition is thermally curedafter application to the substrate. In another embodiment, the coatingcomposition is cured by exposure to ionizing radiation after applicationto the substrate. In yet another embodiment, the coating composition iscured by exposure to actinic radiation after application to thesubstrate, while in another embodiment the coating composition is curedby exposure to (1) ionizing radiation or actinic radiation and (2)thermal energy after application to the substrate.

[0304] The coatings formed from the compositions according to thepresent invention can have outstanding appearance properties and initialscratch (mar) resistance properties, as well as post-weathering or“retained” scratch (mar)resistance, which can be evaluated by measuringthe gloss of coated substrates before and after abrading of the coatedsubstrates.

[0305] In one embodiment, the present invention is directed to methodsof improving the scratch resistance of a substrate comprising applyingto the substrate any of the inventive compositions described for thesubstrate. In another embodiment, the present invention is directed to amethod of improving the dirt repellency of a substrate comprisingapplying to the comprising any of the inventive compositions describedfor the substrate.

[0306] In another embodiment, the present invention is directed to amethod for retaining the gloss of a substrate over time comprisingapplying to the substrate comprising any of the inventive compositionsdescribed for the substrate. In another embodiment, the presentinvention is directed to a method for revitalizing the gloss of asubstrate comprising applying to the substrate any of the inventivecompositions described for the substrate.

[0307] In one embodiment, the present invention is directed to curedcompositions having an initial scratch resistance value such that afterscratch testing greater than 40 percent of initial 20° gloss isretained. In another embodiment, the present invention is directed tocured compositions having an initial scratch resistance value such thatafter scratch testing greater than 50 percent of initial 20° gloss isretained. In another embodiment, the present invention is directed tocured compositions having an initial scratch resistance value such thatafter scratch testing greater than 70 percent of initial 20° gloss isretained.

[0308] In another embodiment, the present invention is directed to curedcompositions having a retained scratch resistance value such that afterscratch testing greater than 30 percent of initial 20° gloss isretained. In another embodiment, the present invention is directed tocured compositions having a retained scratch resistance value such thatafter scratch testing greater than 40 percent of initial 20° gloss isretained. In another embodiment, the present invention is directed tocured compositions having a retained scratch resistance value such thatafter scratch testing greater than 60 percent of initial 20° gloss isretained.

[0309] The initial 20° gloss of a coated substrate according to thepresent invention can be measured with a 20° NOVO-GLOSS 20 statisticalglossmeter, available from Gardner Instrument Company, Inc. The coatedsubstrate can be subjected to scratch testing by linearly scratching thecoating or substrate with a weighted abrasive paper for ten double rubsusing an Atlas AATCC Scratch Tester, Model CM-5, available from AtlasElectrical Devices Company of Chicago, Ill. The abrasive paper is 3M281Q WETORDRYTM PRODUCTION™ 9 micron polishing paper sheets, which arecommercially available from 3M Company of St. Paul, Minn. Panels arethen rinsed with tap water and carefully patted dry with a paper towel.The 20° gloss is measured on the scratched area of each test panel. Thenumber reported is the percent of the initial gloss retained afterscratch testing, i.e., 100%× scratched gloss/initial gloss. This testmethod is fully disclosed in the examples that follow.

[0310] In another embodiment, the present invention is directed to acured coating formed from any of the compositions previously described.In another embodiment, the cured composition is thermally cured. Inanother embodiment, the cured composition is cured by exposure toionizing radiation, while in yet another embodiment, the curedcomposition is cured by exposure to actinic radiation. In anotherembodiment the cured composition is cured by exposure to (1) ionizingradiation or actinic radiation and (2) thermal energy.

[0311] In another embodiment, the compositions of the present inventionalso can be useful as decorative or protective coatings for pigmentedplastic (elastomeric) substrates, such as those described above, ormold-in-color (“MIC”) plastic substrates. In these applications, thecompositions can be applied directly to the plastic substrate orincluded in the molding matrix. Optionally, an adhesion promoter canfirst be applied directly to the plastic or elastomeric substrate andthe composition applied as a topcoat thereover. The compositions of thepresent invention also can be advantageously formulated as pigmentedcoating compositions for use as primer coatings, as basecoats inmulti-component composite coatings, and as monocoat topcoats includingpigments or colorants. The components used to form the compositions inthese embodiments can be selected from the coating components discussedabove, and additional components also can be selected from those recitedabove.

[0312] In another embodiment of the present invention, a transparentthermally-cured composition is provided which comprises a plurality ofparticles within the cured composition. As discussed in greater detailbelow, in such embodiments a first portion of the particles is presentin a surface region of the cured composition in a concentration which ishigher than a concentration of a second portion of particles which ispresent in a bulk region of the cured composition. In certain instances,the BYK Haze value of the cured composition is less than 50, can be lessthan 35, and is often less than 20 as measured using a BYK Haze Glossmeter available from BYK Chemie USA.

[0313] As used herein “surface region” of the cured composition meansthe region which is generally parallel to the exposed air-surface of thecoated substrate and which has thickness generally extendingperpendicularly from the surface of the cured coating to a depth rangingfrom at least 20 nanometers to 150 nanometers beneath the exposedsurface. In certain embodiments, this thickness of the surface regionranges from at least 20 nanometers to 100 nanometers, and can range fromat least 20 nanometers to 50 nanometers. As used herein, “bulk region”of the cured composition means the region which extends beneath thesurface region and which is generally parallel to the surface of thecoated substrate. The bulk region has a thickness extending from itsinterface with the surface region through the cured coating to thesubstrate or coating layer beneath the cured composition.

[0314] In embodiments of the present invention in which the particleshave an average particle size greater than 50 nanometers, the thicknessof the surface region generally extends perpendicularly from the surfaceof the cured coating to a depth equal to three times the averageparticle size of the particles, and this surface can extend to a depthequal to two times the average particle size of the particles.

[0315] The concentration of particles in the cured coating can becharacterized in a variety of ways. For example, the average numberdensity of particles (i.e., the average number or population ofparticles per unit volume) within the surface region is greater than theaverage number density within the bulk region. Alternatively, theaverage volume fraction (i.e., volume occupied by particles/totalvolume) or average weight percent per unit volume, i.e., ((the weight ofparticles within a unit volume of cured coating)/(total weight of theunit volume of cured coating))×100% of the particles within the surfaceregion is greater than the average volume fraction or average weightpercent of particles within the bulk region.

[0316] The concentration of particles (as characterized above) presentin the surface region of the cured coating can be determined, ifdesired, by a variety of surface analysis techniques well known in theart, such as Transmission Electron Microscopy (“TEM”), Surface ScanningElectron Microscopy (“X-SEM”), Atomic Force Microscopy (“AFM”), andX-ray Photoelectron Spectroscopy.

[0317] For example, the concentration of particles present in thesurface region of the cured coating may be determined by cross-sectionaltransmission electron microscopy techniques. A useful transmissionelectron microscopy method can be described generally as follows. Acoating composition is applied to a substrate and cured under conditionsappropriate to the composition and substrate. Samples of the curedcoating are then removed or delaminated from the substrate and embeddedin a cured epoxy resin using techniques as are well known in the art.The embedded samples can then be microtomed at room temperature usingtechniques well known in the art, such as by forming a block face. Thesections can be cut using a 45° C. diamond knife edge mounted in aholder with a “boat cavity” to hold water. During the cutting process,sections float to the surface of the water in the boat cavity. Once afew cuts reach an interference color of bright to dark gold (i.e.approximately 100 to 150 nanometers thickness), individual samplestypically are collected onto a formvar-carbon coated grid and dried atambient temperature on a glass slide. The samples are then placed in asuitable transmission electron microscope, such as a Philips CM12 TEM,and examined at various magnifications, such as at 105,000×magnification, for documentation of particle concentration at thesurface region, via electron micrography. The concentration of particlesin a surface region of a cured coating can be ascertained upon visualinspection of the electron micrograph, and FIG. 4 provides an example ofsuch an electron micrograph.

[0318] It should be understood that the particles can be present in thesurface region such that a portion of the particles at least partiallyprotrudes above the cured coating surface, essentially unprotected by anorganic coating layer. Alternatively, the particles can be present inthe surface region such that this organic coating layer lies between theparticles and the exposed air-surface interface of the surface region.

[0319] In certain embodiments, the cured composition or coating of thepresent invention has an initial 20° gloss (as measured using a 20°NOVO-GLOSS 20 statistical glossmeter, available from Gardner InstrumentCompany) of greater than 70, can be greater than 75, and is oftengreater than 80. This high gloss composition can be curable underambient or thermal conditions or by radiation curing techniques, forexample, by actinic radiation. In one embodiment, the high glosscomposition is curable by ambient or thermal conditions.

[0320] Moreover, the cured topcoat can exhibit excellent initial scratch(mar) resistance as well as post-weathering scratch (mar) resistanceproperties. The cured topcoat can have an initial scratch (mar)resistance value (as measured by first determining the initial 20° glossas described above, linearly abrading the cured coating surface with aweighted abrasive paper for ten double rubs using an Atlas AATCC ScratchTester, Model CM-5, available from Atlas Electrical Devices Company, andmeasuring the 20′ gloss as described above for the abraded surface) suchthat after scratch (mar) testing greater than 50 percent of initial 20°gloss is retained, in certain instances greater than 60 percent ofinitial 20° gloss is retained, and in other instances greater than 70percent of initial 20° gloss is retained after abrading the coatingsurface (that is, 100%× scratched gloss/initial gloss).

[0321] Also, the cured topcoat of the present invention can have apost-weathering scratch (mar) resistance (as measured using the scratchtest method described above after the unscratched test panels weresubjected to simulated weathering by QUV exposure to UVA-340 bulbs in aweathering cabinet available from Q Panel Company) such that greaterthan 50 percent of initial 200 gloss is retained after weathering. Inanother embodiment, greater than 60 percent of initial 20° gloss isretained, an often greater than 70 percent of initial 20° gloss isretained after weathering.

[0322] The cured compositions of the present invention advantageouslycan be employed as the transparent topcoat (clearcoat) in a curedmulti-component composite coating comprising a basecoat deposited from apigmented coating composition and the topcoat deposited from a topcoatcoating composition. When so employed, the cured topcoat can bedeposited from any topcoating composition described above whichcomprises particles, in certain instances having a particle size rangingfrom 1 to 1000 nanometers prior to incorporation into the coatingcomposition. Of course whether the haze is too great will depend uponthe size, composition and shape of the particles.

[0323] In yet another embodiment of the present invention, a compositionis provided which comprises particles within a composition comprisingone or more thermoplastic materials. As previously described, theconcentration of particles is greater in the surface region than in thebulk region. The composition can be derived from a thermoplasticresinous composition. Nonlimiting examples of suitable thermoplasticmaterials include high molecular weight (i.e., Mw greater than 20,000,greater than 40,000, or greater than 60,000), acrylic polymers,polyolefin polymers, polyamide polymers, and polyester polymers suitablefor use in lacquer dry systems. One nonlimiting example of a class ofthermoplastic materials from which the composition can be derived isfluoropolymer-acrylic copolymers such as those prepared frompolyvinylidene fluoride, for example, KYNAR 500 (available from AusimontUSA, Inc.) and thermoplastic acrylic copolymers, such as ACRYLOID B44(65% methyl methacrylate and 35% ethyl acrylate), available from DockResin, Inc.

[0324] In certain embodiments, the cured composition or coating of thepresent invention has an initial 20° gloss (as measured using a 20°NOVO-GLOSS 20 statistical glossmeter, available from Gardner InstrumentCompany) of greater than 70, can be greater than 75, and is oftengreater than 80. This high gloss composition can be curable underambient or thermal conditions or by radiation curing techniques, forexample, by actinic radiation. In one embodiment, the high glosscomposition is curable by ambient or thermal conditions.

[0325] In another embodiment, the present invention is directed to amethod for retaining the gloss of a polymeric substrate or polymercoated substrate after a predetermined period of time comprisingapplying to the substrate comprising any of the inventive compositionsdescribed for the substrate. This predetermined period of time cangenerally be at least 6 months and can be at least one year. In anotherembodiment, the present invention is directed to a method forrevitalizing the gloss of a polymeric substrate or polymer coatedsubstrate comprising applying to the substrate any of the inventivecompositions described above.

[0326] Illustrating the invention are the following examples which,however, are not to be considered as limiting the invention to theirdetails. Unless otherwise indicated, all parts and percentages in thefollowing examples, as well as throughout the specification, are byweight.

EXAMPLES

[0327] Example A describes the preparation of a polysiloxane polyolwhich is the hydrosilylation reaction product of a pentasiloxanecontaining silicon hydride and trimethylolpropane monoallyl ether.Example B describes the preparation of a carbamate functionalgroup-containing polysiloxane using the polysiloxane of Example A as astarting material. Example C describes the preparation of a carbamatefunctional group-containing polysiloxane using a commercially availablehydroxyl functional polysiloxane.

[0328] Examples AA, BB, CC, DD and EE describe the preparation ofvarious silica dispersions which are subsequently incorporated intocoating compositions.

[0329] Examples 1 through 10 describe the preparation of one-packcoating compositions which contain aminoplast curing agents.

[0330] Comparative Examples 1 through 3 describe the preparation of highsolids coating compositions which were used to form the transparenttopcoats in comparative multi-component composite coating compositions.The composition of Example 1 contains no polysiloxane and no inorganicparticles, and the compositions of Examples 2 and 3 contain nopolysiloxane but include inorganic particles in the form of a colloidalsilica dispersion.

[0331] Examples 4 and 5 describe the preparation of coating compositionsof the invention which contain a carbamate functional group-containingpolysiloxane and inorganic particles in the form of a colloidal silicadispersion. Example 6 describes the preparation of a coating compositionof the invention which contains a carbamate functional group-containingpolysiloxane and inorganic particles in the form of colloidal silicawithin the polysiloxane. Example 7 describes the preparation of thecoating composition which is the nonsilica containing analog of Example6. Example 8 describes the preparation of a coating composition whichcontains a carbamate functional group-containing siloxane different fromthat used in the examples above. Example 10 describes the preparation ofa film forming composition of the invention which contains inorganicparticles in the form of a fumed silica dispersion prepared by grindingthe fumed silica in the presence of a polysiloxane prior toincorporation into the composition.

[0332] Examples 11 through 17 describe the preparation of coatingcompositions which are prepared as two-component systems, i.e., thecompositions comprise a polyisocyanate curing agent which is added tothe compositions just prior to application.

[0333] Comparative Example 11 describes the preparation of a coatingcomposition used to form the transparent topcoat in a multi-componentcomposite coating composition which contains an acrylic polyol and apolyisocyanate curing agent. Comparative Example 12 describes thepreparation of the acid catalyst containing analog of Example 11.Comparative Example 13 describes the preparation of the aminoplastcontaining analog of Example 11 and Comparative Example 14 describes thepreparation of the acid catalyst containing analog of Example 13.Example 15 describes the preparation of a coating composition of theinvention which contains the acrylic polyol, both aminoplast andpolyisocyanate curing agents and a polysiloxane polyol. Example 16 isthe acid catalyst containing analog of Example 15. Example 17 describesthe preparation of a coating composition of the invention which containsan acrylic polyol, both aminoplast and polyisocyanate curing agents,acid catalyst, the polysiloxane polyol and inorganic particles in theform of a colloidal silica dispersed in the polysiloxane polyol. Example18 is the analog of Example 17, but containing a higher level of thecolloidal silica.

[0334] Examples 19 and 20 describe the preparation of respectiveone-component and two-component coating compositions of the presentinvention which are suitable for application to flexible elastomericsubstrates.

[0335] Example 21 describes the preparation of epoxy/acid coatingcompositions. Examples 21A and 21B describe the preparation ofcomparative compositions which contain no inorganic particles andExamples 21C-21D describe the preparation of coating compositions of theinvention which contain varying amounts of the inorganic particles.

[0336] Examples 22A to 22I describe the preparation of two-componentcoating compositions which illustrate the effects of lower levels ofvarious polysiloxanes in conjunction with inorganic particles in theform of colloidal silica.

[0337] Example 23 describes the preparation of transparent topcoatcoating compositions of the present invention (Examples 23A-23C) whichwere applied to respective substrates and subsequently evaluated usingtransmission electron microscopy.

[0338] Example 24 describes the preparation of coating compositions ofthe present invention which contain various polysiloxanes in conjunctionwith inorganic particles in the form of colloidal silica. The coatingcomposition was applied to a basecoated substrate and evaluated versus asimilarly applied commercial two-component isocyanate clearcoat(comparative example) for penetration (scratch depth) as a function ofload and scratch distance to determine the critical load at whichcoating failure occurs.

[0339] Example 25 describes the preparation of coating compositions ofthe present invention which contain various levels of the polysiloxanepolyol of Example A (Examples 25B to 25G) in conjunction with variouslevels of inorganic particles in the form of colloidal silica.Comparative Example 24A contains polysiloxane polyol but no colloidalsilica.

[0340] Example 26 describes the preparation of coating compositions ofthe present invention in solid particulate form (i.e., powder coatingcompositions, Examples 26C and 26D) which contain surface active agentsin conjunction with inorganic particles in the form of aluminum oxide.Comparative Examples 26A and 26B describes powder compositions whichcontain surface active agents but no aluminum oxide.

[0341] Example 27 describes the preparation of transparent topcoatcoating compositions of the present invention.

[0342] Example 28 describes the preparation of coating compositions ofthe present invention which contains silylated compounds.

[0343] Example 29 describes the preparation of a coating composition ofthe present invention which is cured via a dual cure system.

[0344] Example 30 describes the preparation of a coating compositions ofthe present invention.

[0345] Example 31 describes the preparation of coating compositions ofthe present invention.

Polysiloxanes EXAMPLE A

[0346] This example describes the preparation of polysiloxane polyol, aproduct of the hydrosilylation of pentasiloxane with an approximatedegree of polymerization of 3 to 4, i.e., (Si—O)₃ to (Si—O)₄. Thepolysiloxane polyol was prepared from the following mixture ofingredients: Equivalent Parts By Weight Ingredients Weight Equivalents(kilograms) Charge I: Trimethylolpropane 174.0 756.0 131.54 monoallylether Charge II: MASILWAX BASE¹ 156.7² 594.8 93.21 Charge III:Chloroplatinic acid  10 ppm Toluene 0.23 Isopropanol 0.7 # from BASFCorporation.

[0347] To a suitable reaction vessel equipped with a means formaintaining a nitrogen blanket, Charge I and an amount of sodiumbicarbonate equivalent to 20 to 25 ppm of total monomer solids was addedat ambient conditions and the temperature was gradually increased to 75°C. under a nitrogen blanket. At that temperature, 5.0% of Charge II wasadded under agitation, followed by the addition of Charge III,equivalent to 10 ppm of active platinum based on total monomer solids.The reaction was then allowed to exotherm to 95° C. at which time theremainder of Charge II was added at a rate such that the temperature didnot exceed 95° C. After completion of this addition, the reactiontemperature was maintained at 95° C. and monitored by infraredspectroscopy for disappearance of the silicon hydride absorption band(Si—H, 2150 cm⁻¹).

EXAMPLE B

[0348] This Example describes the preparation of a carbamate-functionalpolysiloxane using the polysiloxane polyol of Example A.

[0349] A suitable reaction vessel equipped for vacuum distillation wasflushed with N₂. To the reaction flask was added 1782.9 g ofpolysiloxane polyol of Example A, 5.48-g of butyl stannoic acid and16.41 g triphenyl phosphite. The reaction was placed under vacuum andheated to a temperature of 140° C. To the resulting mixture was addedover a period of 3 hours, 665.4 g of a 38% solution of1-methoxy-2-propyl carbamate in 1-methoxy-2-propanol. After the additionwas completed the temperature was increased to 150° C. and held untildistillation was complete. The reaction was cooled to a temperature of90° C. and brought to atmospheric pressure. The resulting resin wasdiluted with 825.3 g of 1-methoxy-2-propanol.

EXAMPLE C

[0350] This Example describes the preparation of a carbamate-functionalpolysiloxane. A suitable reaction vessel equipped with stirrer,temperature probe, distillation condenser and receiver was flushed withN₂. To the reaction vessel was added 291.9 grams of KR-2001, apolysiloxane available from Shin-Etsu Chemicals, 1.91 grams of butylstannoic acid and 250.4 grams of xylene. The reaction mixture was heatedto a temperature of 140° C. at which time 148.6 grams of methylcarbamate was added over a period of 1 hour. The reaction was held atthat temperature for a period of 3.5 hours.

Silica Dispersions EXAMPLE AA

[0351] This Example describes the preparation of a colloidal silicadispersion. The dispersion was prepared as follows:

[0352] To a suitable reaction vessel equipped for vacuum distillationand flushed with N₂ was added 811.9 g of an 88% acrylic polyol solution(40%/1 hydroxy propyl acrylate, 60% butyl methacrylate) in1-methoxy-2-propanol; 544.3 g of colloidal silica (available asORGANOSILICASOL MT-ST from Nissan Chemical Co.); 1.58 g of butylstannoic acid and 3.18 g triphenyl phosphite. The reaction was placedunder vacuum and heated to 140° C. To the resulting mixture was added,over a period of 3 hours, 665.4 g of a 38% solution of1-methoxy-2-propyl carbamate in 1-methoxy-2-propanol. After the additionwas complete, the temperature was increased to 150° C. and held at thattemperature until distillation had stopped. The reaction was cooled to90° C. and brought to atmospheric pressure. The resulting resin had ahydroxyl value of 80.51 and was diluted with 251.4 g of1-methoxy-2-propanol.

EXAMPLE BB

[0353] This Example describes a colloidal silica dispersion prepared asdescribed in Example 5 of U.S. Pat. No. 5,853,809 as follows: To asuitable reaction vessel equipped with stirrer and temperature probe andflushed with N₂ was added 858.7 g of the carbamate functional acrylicresin. The resin was heated to a temperature of 40° C. To the resultingsolution was added over a period of 20 minutes, 124.4 g ofgamma-isocyanatopropyl triethoxysilane (available as A1310 from OSiSpecialties, a subsidiary of Witco Corporation) diluted in 148.2 g ofamyl acetate and 10.5 g butanol. That temperature was maintained for 3.5hours and the reaction was monitored for completion by infraredspectroscopy. With stirring, 60 g of the resulting resin was added to1500 g of NALCO 1057 (available from Nalco Chemical Co.). The resultingmixture was heated to a temperature of 60° C. and held for a period of19 hours.

[0354] The carbamate functional acrylic resin prepared as follows: Asuitable reaction flask equipped for vacuum distillation was flushedwith N₂ and 1670.2 g of 88% acrylic polyol solution, (40% HPA, 60% BMA),in 1-methoxy-2-propanol, 4.9 g of butyl stannoic acid and 4.9 g oftriphenyl phosphite added. The reaction was placed under vacuum andheated to a temperature of 140° C. To the resulting mixture was added,over a period of 3 hours, 1263.64 g of a 38% solution of1-methoxy-2-propyl carbamate in 1-methoxy-2-propanol. The resultingdistillate was collected. After the addition was complete, thetemperature was increased to 150° C. and held at that temperature untildistillation had stopped. The reaction was cooled to 90° C. and broughtto atmospheric pressure. The resulting resin had a hydroxyl value of34.48 and was diluted with a mixture of 251.4 g of 1-methoxy-2-propanoland 3-ethoxy ethyl propionate.

EXAMPLE CC

[0355] This Example describes a colloidal silica dispersion prepared asfollows: A suitable reaction vessel equipped for vacuum distillation wasflushed with N₂. To the reaction flask was added 509.6 g of thepolysiloxane polyol of Example A, 566.3 g of ORGANOSILICASOL MA-ST-Mcolloidal silica (available from Nissan Chemicals), 1.57 g of butylstannoic acid and 4.69 g of triphenyl phosphite. The reaction was placedunder vacuum and heated to 140° C. To the resulting mixture was addedover a period of 3 hours 997.9 g of a 38% solution of 1-methoxy-2-propylcarbamate in1-methoxy-2-propanol. The resulting distillate wascollected. After the feed was complete, the temperature was increased to150° C. and held until distillation was complete. The reaction wascooled to 90° C. and brought to atmospheric pressure. The resultingdispersion was diluted with 160.8 g of 1-methoxy-2-propanol.

EXAMPLE DD

[0356] This Example describes a colloidal silica dispersion prepared asfollows: A suitable reaction vessel equipped for vacuum distillation wasflushed with N₂. To the reaction flask was added 150.7 g of thepolysiloxane polyol of Example A and 500.4 g of ORGANOSILICASOL MT-ST,colloidal silica (available from Nissan Chemicals). The resultingmixture was vacuum distilled at 25° C. for a period of 2 hours and thendiluted with 160.8 g of methyl amyl ketone.

EXAMPLE EE

[0357] This Example describes a fumed silica dispersion prepared asfollows: A suitable mixing container was equipped with a Cowlesdispersing agitator. To the container was added 315.3 g of thepolysiloxane polyol of Example A, 451.0 g of methyl amyl ketone and135.2 g of R812 fumed silica (available from Degussa Corporation). Themixture was agitated until all of the R812 silica was dispersed. Thedispersion was then added to an EIGER Mill for a period of 60 minutes toachieve a grind fineness of 8+Hegman.

Coating Compositions

[0358] The following Examples 1-10 describe the preparation of coatingcompositions of the invention, as well as comparative coatingcompositions, used to form the transparent topcoat in multi-componentcomposite coating compositions. Amounts indicated represent parts byweight. The coating compositions were prepared from a mixture of thefollowing ingredients. Example Example Example Example Example ExampleExample Example Example Example INGREDIENT 1* 2* 3* 4 5 6 7 8 9 10Methyl amyl 35.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0 40.0 ketoneTINUVIN 928¹ 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 3.0 TINUVIN 123² 0.500.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 1.00 RESIMENE 757³ 41.24 41.2441.24 41.24 41.24 41.24 41.24 41.24 41.24 41.24 Flow additive⁴ 0.50 0.500.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Catalyst⁵ 1.43 1.43 1.43 1.431.43 1.43 1.43 1.43 1.43 — Catalyst⁶ — — — — — — — — — 2.50 Carbamate-93.75 70.17 93.34 69.91 46.73 70.31 70.31 70.31 65.63 70.31 functionalacrylic resin⁷ Silica dispersion — 23.87 — — 23.87 — — — — — of ExampleAA Silica dispersion — — 10.40 10.40 — — — — — — of Example BB Silicadispersion — — — — — 15.09 — — — — of Example CC Silica dispersion — — —— — — — — 9.23 — of Example DD Silica dispersion — — — — — — — — — 33.33of Example EE Carbamate- — — — 18.75 18.75 4.53 18.75 — 18.75 4.91functional polysiloxane of Example B Carbamate- — — — — — — — 27.53 — —functional polysiloxane of Example C # 88% acrylic polyol solution, (40%HPA, 60% BMA), in 1-methoxy-2-propanol, 4.9 g of butyl stannoic acid and4.9 g triphenyl phosphite added. The reaction was placed # under vacuumand heated to a temperature of 140° C. To the resulting mixture wasadded, over a period of 3 hours, 1263.64 g of a 38% solution of1-methoxy-2-propyl # carbamate in 1-methoxy-2-propanol. The resultingdistillate was collected. After the addition was completed, thetemperature was increased to 150° C. and held at # that temperatureuntil distillation had stopped. The reaction was cooled to 90° C. andbrought to atmospheric pressure. # The resulting resin had a hydroxylvalue of 34.48 and was diluted with a mixture of 251.4 g of1-methoxy-2-propanol and 3-ethoxy ethyl propionate.

[0359] Each of the above coating compositions of Examples 1 through 10was prepared as a one-pack coating composition by adding the ingredientsin the order shown and mixing under mild agitation.

[0360] Test Panel Preparation:

[0361] BWB-5555 black waterbome basecoat (commercially available fromPPG Industries, Inc.) was spray applied to steel panels (4 inches×12inches) coated with ED5000, cationic electrodepositable primercommercially available from PPG Industries, Inc. The panels werepre-baked at a temperature of 285° F. for approximately 30 minutes. Eachof the coating compositions of Examples 1 through 10 above was appliedas a transparent topcoat to the basecoated panels (prepared as describedimmediately above) using a 6 mil drawdown bar to form thereon atransparent topcoat. The topcoated panels were allowed to flash atambient temperatures for approximately 5 minutes, then thermally curedat 285° F. for 30 minutes. The multi-component composite coatings weretested for various physical properties including gloss, scratchresistance, hardness and haze.

[0362] Test Procedures:

[0363] Scratch resistance of coated test panel was measured using thefollowing method: Initial 20° gloss of the coated panels is measuredwith a 20° NOVO-GLOSS 20 statistical glossmeter, available from GardnerInstrument Company, Inc. Coated panels were subjected to scratch testingby linearly scratching the coated surface with a weighted abrasive paperfor ten double rubs using an Atlas AATCC Scratch Tester, Model CM-5,available from Atlas Electrical Devices Company of Chicago, Ill. Panelswere then rinsed with water and carefully patted dry. The 20° gloss wasmeasured on the scratched area of each test panel. The number reportedis the percent of the initial gloss retained after scratch testing,i.e., 100%× scratched gloss/initial gloss. Post-weathering scratchresistance (retained scratch resistance) was measured using the scratchtest method described above after the unscratched test panels weresubjected to simulated weathering by QUV exposure to UVA-340 bulbs in aweathering cabinet available by Q Panel Co. Testing was as follows acycle of 70° C. for 8 hours followed by 50° C. for 4 hours (totalexposure time of 100 hrs). The number reported is the percent of theinitial gloss retained after post-weathering scratch testing, i.e., 100×post-weathering scratched gloss/initial gloss.

[0364] Film hardness of the multi-layer composite coatings was measuredusing a TUKON Hardness Tester according to ASTM-D1474-92 to give KnoopHardness values. Higher reported values indicate harder coatingsurfaces.

[0365] The degree of haziness or lack of film clarity of the transparenttopcoat was measured using BYK HAZE/GLOSS instrument from BYK Chemical.Higher numbers indicate a higher degree of haziness or lack of clarity.Test results are provided in the following Table 1. TABLE 1 % Initial20° % Initial 20° Gloss Retained 20° Gloss After Post-Weathering GlossMar/Scratch Mar/Scratch Knoop Example (Initial) Test Test Hardness BykHaze 1 89 26% 25% 10.9 14 2 89 58% 30% 12.1 18 3 88 82% 86% 11.2 19 4 5082% 62% 12.1 294Haze 5 89 85% 28% 11.8 19 6 87 95% 94% 12.1 14 7 89 80%22% 11.9 14 8 91 69% 31% 10.9 14 9 88 95% 93% 11.2 14 10 86 97% 92% — —

[0366] The results reported in Table 1 above illustrate that themulti-component composite coating compositions of the invention ofExamples 4-10 provide coatings with good Knoop film hardness and initialand retained scratch resistance after simulated weathering testing.

EXAMPLES 11-18

[0367] The following describes the preparation of coating compositionsprepared as two-pack systems, that is, a polyisocyanate curing agent wasadded to the remaining ingredients just prior to application. Thetwo-pack systems were prepared from a mixture of the ingredients listedbelow. Amounts indicated for each component are expressed in grams totalweight. Example Example Example Example Example Example Example ExampleIngredients 11* 12* 13* 14* 15 16 17 18 Methyl amyl ketone 20.0 20.020.0 20.0 20.0 20.0 20.0 40.0 Acrylic polyol¹ 89.6 89.6 89.6 89.6 43.343.3 43.3 CYMEL 202² — — 18.8 18.8 18.8 18.8 18.8 18.8 Acid catalyst³ —1.3 — 1.3 — 1.3 1.3 1.3 Polysiloxano polyol — — — — 23.4 23.4 20.9 13.4of Example 4 Silica dispersion⁴ — — — — — — 7.7 30.8 DESMODUR N-3390⁵41.4 41.4 24.8 24.8 33.3 33.3 33.3 33.3

[0368] TABLE 2 % Initial 20° % Initial 20° Gloss Retained Initial GlossAfter Post-Weathering 20° Mar/Scratch Mar/Scratch Knoop Example GlossTest Test Hardness Byk Haze 11 88 17% 22% 10.9 11 12 88 15% 19% 10.0 1113 90 30% 21% 10.9 10 14 92 57% 48% 13.9 11 15 88 47% 14% 10.0 14 16 8988% 66% 9.8 15 17 86 98% 97% 11.8 18 18 84 98% 98% 10.5 18

[0369] The data presented in Table 2 above illustrate that the coatingcompositions of Examples 15-18 of the present invention exhibit goodinitial and retained scratch resistance properties after simulatedweathering.

EXAMPLE 19

[0370] This example describes the preparation of a one-component coatingcomposition used to form the transparent topcoat in a multi-componentcomposite composition of the present invention suitable for applicationto a flexible elastomeric substrate. The film forming compositioncontains a hydroxyl functional group-containing polysiloxane andinorganic particles in the form of a colloidal silica. The coatingcomposition was prepared from a mixture of the following ingredientsunder agitation in the order which they appear: Resin Silica Weight inIngredients Solids Solids Grams 2-Methoxy propyl acetate 2.7 Methyl amylketone 40.0 TINUVIN 928 3.0 3.0 TINUVIN 123 0.5 0.5 Carbamate functionalacrylic¹ 21.5 33.6 Carbamate functional polyester² 21.5 30.7 Carbamatefunctional polyether³ 10.0 10.3 Silica dispersion⁴ 7.0 3.0 12.8 RESIMENE757 40.0 41.2 Flow additive of Comparative 0.3 0.5 Example 1 Catalystsolution⁵ 1.0 2.5 # suitable flask was added 3652.5 g of 90% acrylicpolyol solution (40% HPA, # 58% BMA, 2% methyl styrene dimer) in1-methoxy-2-propanol, 2836.2 grams of # a 38% solution of1-methoxy-2-propyl carbamate in 1-methoxy-2-propanol, # 25.0 grams of1-methoxy-2-propanol, 9.6 grams triphenyl phosphite, and # 2.4 gramsbutyl stannoic acid. The materials were mixed and then transferred #over a period of 7.3 hours into a reactor vessel suitable for vacuum #distillation. During the transfer, the temperature of the reactor was #held between 131° C. and 139° C., and reduced pressure was # maintainedto ensure steady distillation of 1-methoxy-2-propanol. Upon # completionof the transfer, pressure was gradually reduced to maintain #distillation until a final pressure of 41 mm Hg was reached. When #distillation was completed, the resulting resin was cooled and thinned #with 925 g 1-methoxy-2-propanol and 950 g ethyl 3-ethoxypropionate.Prior # to thinning, the resin had a measured hydroxyl value of 40.8.After thinning, # the resin had a measured solids content of 63%, aweight average molecular # weight of 9107, and a number averagemolecular weight of 3645 as determined # by gel permeationchromatography vs. a polystyrene standard. # was prepared from2,2,4-trimethyl-1,3-pentanediol/trimethylolpropane/neopentyl #glycol/hexahydrophthalic anhydride (22.7/10.6/17.5/49.2 weight ratio)with a # resulting hydroxyl value of 146 and at 100% solids. To areactor equipped with # a thermocouple, overhead stirrer, nitrogeninlet, and reflux condenser was added # 375.1 parts by weight of thepolyester as prepared immediately above, 71.9 parts # methyl carbamate,1.0 parts butyl stannoic acid, 0.8 parts triphenyl phosphite, # and 35.0parts 2-methoxy-1-propanol. The reactants were heated to reflux under #nitrogen blanket at 141° C. and held for 1 hour. Then, the refluxcondenser # was removed and the reactor equipped for distillation atatmospheric pressure. The # temperature was gradually increased to 151°C. until 28.7 parts of distillate # were collected. The mixture was thencooled to 145° C. and the reactor equipped # for vacuum distillation.Distillation continued under reduced pressure until 60 mmHg # wasattained. A total distillate of 78.3 parts was collected. The resultingresin # hydroxy value was 33.8 at 100% solids. The resin was cooled anddiluted with 140 # parts 2-methoxy-1-propanol. The final resin solutionwas 72.2% solids with a weight # average molecular weight of 2197 andnumber average molecular weight of 1202 as # determined by gelpermeation chromatography using polystyrene standards. # for vacuumdistillation was flushed with N₂. To the reaction flask was added #1051.1 g of siloxane polyol from Example A, 1125.8 g of ORGANOSILICASOLMT-ST-M # colloidal silica from Nissan Chemicals and 480.3 g of methylamyl ketone. The # resulting mixture was vacuum distilled at 25° C. for4 h. # amine/51.1 g ethanol/31.2 g isopropanol.

EXAMPLE 20

[0371] This example describes the preparation of a two-component coatingcomposition used to form a transparent topcoat in a multi-componentcomposite composition of the present invention. The film formingcomposition contains both aminoplast and polyisocyanate curing agents,hydroxyl functional group-containing polysiloxane and inorganicparticles in the form of a colloidal silica. The coating composition wasprepared from a mixture of the following ingredients under agitation inthe order which they appear: Resin Silica Weight in Ingredients SolidsSolids Grams Methyl amyl ketone 35.0 Ethyl 3-ethoxy propionate 11.9Silica dispersion of Example 19 4.7 2.0 8.6 TINUVIN 928 3.0 3.0 CYMEL202 15.0 18.8 Acrylic polyol¹ 23.6 47.2 Polyester polyol² 20.3 25.3Hydroxyl containing polysiloxane 10.4 10.4 of silica dispersion inExample 19 TINUVIN 292³ 0.5 0.5 Flow additive of Example 1 0.3 0.5 Thefollowing two ingredients were added to the above mixture immediatelyprior to application of the coating: DESMODUR N-3390 26.0 28.9 Catalystof Example 12 1.0 1.3 # 51% in 1:1 xylene/butyl acetate, having a weightaverage molecular weight of 7200, a # number average molecular weight of2850 based on gel permeation chromatography using # polystyrenestandards. # hexane diol/18.6% trimethylol propane/18.4% adipicacid/8.1% trimethyl pentane diol), # 80% in 60:40 butyl acetate/Solvesso100, having a hydroxy value of 145 and a Gardner-Holte # viscosity ofX-Z

[0372] Test Panel Preparation:

[0373] MPP4100D, high solids adhesion promoter commercially availablefrom PPG Industries, Inc., was applied to SEQUEL 1440 TPO plaques,commercially available from Standard Plaque (4 inches×12 inches), byhand spraying at a dry film thickness of 0.15 mils to 0.25 mils (3.8microns to 6.4 microns). Each Sequel 1440 plaque was cleaned withisopropyl alcohol prior to being treated. The treated Sequel 1440plaques were allowed to stand for one day before a solventborne blackbasecoat commercially available from PPG Industries, Inc., eitherCBCK8555A (used in conjunction with 2K clearcoats) or CBC8555T (used inconjunction with 1 K clearcoats), was applied at a dry film thickness of0.8 mils to 1.0 mils (20.3 microns to 25.4 microns). CBCK8555A andCBC8555T basecoats were applied by spraymation in two coats with a 90second Aflash-dry” period at ambient temperatures between each coat. Thebasecoated panels were flash-dried at ambient temperature for 90 secondsbefore the transparent topcoats described in the above Examples 19 and20 were applied by spraymation in two coats with a 90 second ambientflash between each coat. The transparent topcoats had a dry filmthickness ranging from 1.6 mils to 1.8 mils (40.6 microns to 45.7microns). The topcoated panels were flashed-dried at ambient temperaturefor 10 minutes and then thermally cured at 254° F. (123.3° C.) for 40minutes. The coated test panels sat at ambient temperature for four daysprior to testing.

[0374] The test panels prepared as described immediately above wereevaluated for 20° gloss, scratch resistance and post-weathering scratchresistance using the methods described above for these properties versuscommercial one-pack and two-pack systems.

[0375] Additionally, the coated test panels were tested for flexibilityat 70° F. (21.1° C.). For flex testing, a 1-inch by 4-inch piece was cutfrom the coated test panel. The piece was subjected to a mandrel bendusing a 2 inch diameter steel mandrel, such that the two ends of the4-inch long test piece contacted one another. The test panels were thenrated for flexibility by visual inspection for coating cracking on ascale of 0 to 10. A “10” rating is recorded where there is no visiblepaint cracking; a “9” rating has less than five interrupted short linecracks; an “8” has interrupted line cracks with a maximum of fouruninterrupted line cracks; a “6” has five to ten uninterrupted linecracks; a “4” has more than 15 uninterrupted line cracks; and a “0”represents fracture of the substrate.

[0376] Test results are reported in the following Table 3. TABLE 3 %Initial 20° % Initial 20° 20° gloss retained gloss retained Gloss aftermar/ post- Flexibility EXAMPLE (Initial) scratch test weathering RatingExample 19 86 83 55 8 *Commercial 88 46 11 8 Flexible 1K Clear¹ Example20 85 69 35 10 *Commercial 87 17 8 9 Flexible 2K Clear²

[0377] The data presented in Table 3 above illustrate that the coatingcompositions of Examples 19 and 20 of the present invention, whenapplied to thermoplastic polyolefin (TPO) elastomeric substrates,provide similar initial gloss and flexibility properties compared tocommercial clearcoats without silica or polysiloxane, while providingsuperior post-weathering scratch resistance.

EXAMPLE 21

[0378] This example describes the preparation of epoxy/acid coatingcompositions which contain both a functional group-containingpolysiloxane and inorganic particles in the form of colloidal silica atlevels lower than 1% based on total weight of resin solids in thecompositions. The coating compositions were prepared from a mixture ofthe following ingredients: Example Example Example Example Example 21A*21B* 21C 21D 21E Ingredients: (grams) (grams) grams) (grams) (grams)Methyl amyl ketone 40.0 40.0 40.0 40.0 40.0 CYMEL 202 2.50 — — — —Silica dispersion¹ — — 0.03 0.08 0.17 CYLINK 2000² — 28.30 28.30 28.3028.30 Polybutylacrylate 0.50 0.50 0.50 0.50 0.50 N,N-dimethyl dodecylamine 0.30 0.30 0.30 0.30 0.30 Acrylic resin³ 87.89 87.89 87.89 87.8987.89 Crosslinker⁴ 63.69 63.69 63.69 63.69 63.69 Catalyst of Example 12— 1.30 1.30 1.30 1.30

[0379] The coating compositions of Examples 21A-21 E were applied over ablack basecoat (OBISIDIAN SCHWARTZ basecoat, available from PPGIndustries, Inc,) which had been previously applied to the test panelsand cured for 30 minutes at 285° F. (140.6° C.). The transparent coatingcomposition of each example was drawn down over the cured basecoat usinga 6 mil square drawdown bar and cured for 30 minutes at 285° F. (140.6°C.). TABLE 4 Post-weathering scratch (mar) Initial Post-Mar % resistance% 20° Initial 20° Gloss Initial 20° Example Gloss Retained GlossRetained 21A* 84 14 12 21B* 86 27 23 21C 86 49 42 21D 86 67 58 21E 85 8068

[0380] The data presented in Table 4 above illustrate that the coatingcompositions of Examples 21C-21 E of the present invention providesuperior initial and retained mar resistance when compared tocomparative compositions which contain no inorganic particles orpolysiloxane.

EXAMPLE 22

[0381] This example describes the preparation of two-component coatingcompositions 22A through 22I which illustrate the effects of lower(i.e., ≦2 weight percent) levels of polysiloxane. Comparative Examples22A and 22B contain 0% colloidal silica/0% polysiloxane and 2% colloidalsilica/0% polysiloxane, respectively. Examples 22C-22I describe coatingcompositions which each contain 2 weight % of a polysiloxane.POLYSILOXANES EVALUATED HYDROXYL EQUIVALENT SILOXANE CODE WEIGHTDESCRIPTION Polysiloxane of 190 Reaction product of Example Apentasiloxane containing Si-H with trimethylolpropane monoallyl ether KR2001 252 Hydroxy functional methyl and phenyl siloxane from Shin-EtsuChemical Co. Byk 370 1600 Polyester modified hydroxyfunctionaldimethylpolysiloxane from BYK Chemie Byk 373 701 Polyethermodified hydroxy functionaldimethylpolysiloxane from BYK Chemie Byk 3751870 Polyether-polyester modified hydroxy functionaldimethylpolysiloxane from BYK Chemie Byk 325 0 Polyether modified methylalkylpolysiloxane from BYK Chemie Byk 310 0 Polyester modifieddimethylpolysiloxane from BYK Chemie

[0382] Coating Compositions

[0383] A basecoating composition was prepared from a mixture of thefollowing ingredients: Ingredient Solid Weight (G) Formula Weight (G)Methyl amyl ketone — 31.2 CYMEL 202 15.0 18.8 Acrylic polyol¹ 61.5 102.1Polybutylacrylate 0.3 0.5 DESMODUR N-3390 22.4 24.9 Phenyl acid 1.0 1.3phosphate catalyst # methacrylate/1.96 weight % acrylic acid/1.63 weight% methyl styrene dimer, 60.25% solids # in a solvent blend.

[0384] Each of the coating compositions of Example 22A-22I was preparedby adding the following weight percentages of colloidal silica andpolysiloxane ingredients to 178.8 grams of the coating compositiondescribed immediately above. The coating compositions thus prepared wereapplied and tested as described above for Examples 1-18. % Initial 20°Gloss Initial Retained After Coefficient % Colloidal Siloxane 20°Mar/Scratch of Friction Example Silica¹ % Siloxane Type Gloss Test (μ)22A 0 0 — 86 38% 0.19 22B 2 0 — 86 44% 0.18 22C 2 1.1 Polysiloxane 8489% 0.17 of Example A 22D 2 1.5 KR-2001 85 51% 0.12 22E 2 1.0 Byk-370 8558% 0.07 22F 2 1.0 Byk-373 Too Seedy To Test 22G 2 1.0 Byk-375 76 57%0.04 22H 2 1.0 Byk-325 Too Seedy To Test 22I 2 1.0 Byk-310 84 52% 0.09

[0385] The data reported above illustrate that the coating compositionsof Example 22C of the present invention containing very low levels(i.e., 1.0 weight percent) of the polysiloxane polyol of Example A inconjunction with inorganic particles in the form of colloidal silicaprovide both excellent initial scratch (mar) resistance. Further, thedata illustrate that the inorganic particles and the polysiloxane polyolact synergistically to provide excellent post-weathering scratchresistance.

EXAMPLE 23

[0386] This example describes the preparation of transparent topcoatcoating compositions which, subsequent to application and cure, wereevaluated using transmission electron microscopy surfacecharacterization techniques. Example 23A describes the preparation of atransparent topcoat composition of the present invention containinginorganic particles in the form of colloidal silica in conjunction withthe polysiloxane polyol of Example A, both of which were added asseparate components. Comparative Example 23B describes the preparationof a comparative transparent topcoat composition containing inorganicparticles in the form of colloidal silica, but no polysiloxane. Example23C describes the preparation of a transparent topcoat composition ofthe present invention where the inorganic particles in the form ofcolloidal silica were dispersed in the polysiloxane polyol of Example Aprior to incorporation into the composition.

[0387] Each of the coating compositions were prepared as describedbelow.

EXAMPLE 23A

[0388] Description Solids Total Weight Methyl Amyl Ketone — 66.6 Tinuvin928 3.0 3.0 Colloidal silica¹ 5.0 16.7 Cymel 202 15.0 18.8 Polysiloxanepolyol of Example A 2.0 2.0 Acrylic polyol² 63.0 106.1 Tinuvin 123 1.01.0 Polybutylacrylate 0.3 0.5 Catalyst of Example 12 1.0 1.3 DesmodurN-3390³ 20.0 22.2 # in Dowanol PM acetate, using VAZO 67 (azobis-2,2=−(2-methylbutyronitrile), 4.9% on # total monomer charge as aninitiator): 39.4 parts of hydroxyethyl methacrylate, 2 parts of #acrylic acid, 57 parts of isobutyl methacrylate, and1.6 parts ofα-methylstyrene dimer. # The polymer solution exhibited the followingproperties: 60% solids contents; 82.4 OH value; # molecular weight. 7410(Mw). # from Bayer Corporation

EXAMPLE 23B

[0389] Description Solids Total Weight Methyl Amyl Ketone — 66.2 Tinuvin928 3.0 3.0 ORGANOSILICASOL MT-ST 5.0 16.7 Cymel 202 15.0 18.8 Acrylicpolyol of Example 23A 65.7 110.7 Tinuvin 123 1.0 1.0 Polybutylacrylate0.3 0.5 Catalyst of Example 12 1.0 1.3 Desmodur N-3390 19.3 21.4

EXAMPLE 23C

[0390] Description Solids Total Weight Methyl amyl ketone — 25.0 Silicadispersion¹ 6.7 8.6 Tinuvin 928 3.0 3.0 Acrylic polyol² 35.9 65.3Tinuvin 292 0.5 0.5 Polybutylacrylate 0.3 0.5 Polysiloxane polyol of15.3 15.3 Example A Cymel 202 15.0 18.8 Catalyst of Example 12 0.5 0.7Desmodur N-3300³ 29.1 29.1 # added 3151.4 g of polysiloxane polyol ofExample A, 4501.9 of colloidal silica (ORGANOSILICASOL MT-ST, available# from Nissan Chemicals) and 1440.6 g of methyl amyl ketone. Theresulting mixture was vacuum distilled. # from PPG Industries, Inc.

Test Panel Preparation for Examples 23A and 23B:

[0391] A black basecoat, SMARAGDSCHWARZ MICA, available from PPG (B&K)Germany, was spray applied to steel test panels (4″×12″ panelscommercially available from ACT Laboratories, Inc. of Hillsdale, Mich.)which had been coated with ED-5000 electrocoat primer and GPXH-5379primer surfacer (both commercially available from PPG Industries, Inc.)using spraymation. The basecoat was applied in two coats with a no flashbetween coats followed by a five minute heated flash at 200° F. beforeapplication of the clearcoats. The basecoat had a dry film thickness of0.47 mils (11.75 micrometers). The coating compositions of Examples 23Aand 23B were spray-applied to the cured basecoats in two coats with a60-second flash between coats followed by 5 minute ambient flash priorto curing for 30 minutes at 285° F. (140.6° C.). Each clearcoat had adry film thickness of approximately 2.1 mils (54.5 micrometers).

Test Panel Preparation for Example 23C:

[0392] A black basecoat, OBSIDIAN SCHWARTZ, available from PPG (B&K)Germany was spray applied and cured as described immediately above forExamples 23A and 23B. The coating composition of Example 23C was appliedto the basecoat as a clearcoat and cured using the procedure describedabove for the clearcoats of Example 23A and 23B. The basecoat had a dryfilm thickness of 0.5 mils (12.5 micrometers) and the clearcoat had adry film thickness of 1.44 mils (36 micrometers).

[0393] Cross-Sectional Transmission Electron Microscopy

[0394] Cured coating samples were delaminated from the substrate andembedded in epoxy using an EPONATE 812 epoxy embedding kit availablefrom Ted Pella's Inc. in a polyester bottle cap mold. Once heat set,samples were removed from the molds and were cut using an X-ACTO razorsaw, extra fine tooth #75350 to a size of approximately 1.5centimeters×1 centimeter. The sized samples were then microtomed atambient temperature using a, RMC MY6000XL microtome using a vice clampspecimen holder. Microtome sections were cut using a 45° diamond knifeedge mounted in a holder with a water-filled boat cavity. Cuts were madeto an interference color of bright to dark gold color (approximately 100nanometers to 150 nanometers), then individual cut specimens werecollected onto a TEM formvar-carbon coated grid. Excess water wasremoved with filter paper and the thin sections were air-dried atambient temperature on a glass microscope slide. Sections were sorted byinterference color thickness. The coating specimens were oriented on theglass slides to permit tilting on axis such that a perpendicularcross-section could be observed. Samples were placed in a Philips CM12TEM operated at a 100 KV accelerating voltage, in transmission mode,using a standard tungsten filament and examined at variousmagnifications for documenting of coating surface morphologies andparticle concentration by visual observation. Kodak SO-163 electronimage film was used to create electron micrograph negatives and thenegatives subsequently developed.

[0395]FIG. 1 is an electron micrograph of a transmission electronmicroscopy image (30,000× magnification) of a cross-section of a curedtransparent topcoat composition of Example 23A which contains bothcolloidal silica and polysiloxane added as separate components. Uponvisual inspection, it can be observed that the concentration ofparticles in the form of colloidal silica lb at the surface region ofthe cured composition, that is, a region extending from the exposedair-surface interface 1 a to a cured coating depth of 20 to 50nanometers (1 millimeter=approximately 30 nanometers) below the exposedsurface is greater than the concentration of colloidal silica 1 c withina bulk region of the cured composition. It should also be noted that theparticles 1 b and 1 c exist as agglomerates within the polymer matrix,rather than as discrete monodispersed particles.

[0396]FIG. 2 is an electron micrograph of a transmission electronmicroscopy image (30,000× magnification) of a cross-section of the curedcomparative transparent topcoat coating composition of Example 23B whichcontains colloidal silica but not polysiloxane. Upon visual inspection,it can be observed that the concentration of particles in the form ofcolloidal silica 2 b at the surface region of the comparative curedcomposition, that is, a region extending from the exposed air-surfaceinterface 2 a to a cured coating depth of 20 to 50 nanometers (1millimeter=approximately 30 nanometers) below the exposed surface isless than the concentration of colloidal silica 2 c within a bulk regionof the cured composition. In fact, there is essentially no colloidalsilica observed in the surface region. It should also be noted that theparticles 2 b and 2 c appear as agglomerates within the polymer matrix,rather than as discrete monodispersed particles.

[0397]FIG. 3 is an electron micrograph of a transmission electronmicroscopy image of a cross-section of the cured transparent topcoatcoating composition of Example 23A (see FIG. 1) viewed at amagnification of 54,000×.

[0398]FIG. 4 is an electron micrograph of a transmission electronmicroscopy image (105,000× magnification) of a cross-section of apreferred cured transparent topcoat coating composition of the presentinvention which contains a pre-formed dispersion of colloidal silica anda polysiloxane. Upon visual inspection, it clearly can be observed thatthe concentration of particles in the form of colloidal silica 4 b atthe surface region of the cured composition that is, a region extendingfrom the exposed air-surface interface 2 a to a cured coating depth of20 to 50 nanometers below the exposed surface, is greater than theconcentration of colloidal silica 4 c within a bulk region of the curedcomposition. It should also be noted that the particles 4 b and 4 cappear as discrete monodispersed particles distributed within thepolymer matrix, rather than as agglomerated particles (compare FIGS. 1and 2).

EXAMPLE 24

[0399] In this example, a coating composition of the present inventionwhich contains inorganic particles in the form of colloidal silicapre-dispersed in a functional group-containing polysiloxane wasevaluated versus a comparative commercial two-component isocyanateclearcoat for coating penetration (scratch depth) as a function of loadand scratch distance.

EXAMPLE 24A

[0400] A coating composition of the present invention was prepared froma mixture of the following ingredients: Total Weight Ingredient Solids(grams) Methyl amyl ketone — 25.0 Silica dispersion¹ 6.7 8.6 TINUVIN 9283.0 3.0 Acrylic polyol of 40.9 74.4 Example 23C TINUVIN 292 0.5 0.5Polybutylacrylate flow 0.3 0.5 additive Polysiloxane polyol of 10.3 10.3Example A CYMEL 202 15.0 18.8 Catalyst of Example 12 0.5 0.7 DESMODURN-3300 29.1 29.1

EXAMPLE 24B

[0401] A black waterborne basecoat was prepared from a mixture of thefollowing ingredients: Solids Total Weight Ingredients (grams) (grams)PROPASOL B¹ — 45.0 CYMEL 327² 35.0 38.9 TINUVIN 1130³ 3.2 3.2 Phosphatedepoxy⁴ 0.5 0.8 Dimethylethanolamine — 2.0 (50% in water) Latex⁵ 46.5109.4 Mineral spirits — 8.0 Water-reducible urethane⁶ 10.0 42.6 Blackpigment dispersion⁷ 11.5 47.6 Dimethylethanolamine — 1.0 (50% in water)Deionized water — 57.5 # from Ciba Geigy Corporation. # PPG Industries,Inc.. # PPG Industries, Inc.

[0402] Test Panel Preparation:

[0403] Steel substrate test panels (available from ACT Laboratories,Inc.) were coated with ED-5000 electrocoat primer (available from PPGIndustries, Inc.). The basecoat of Example 24B above was spray appliedto the primed panels in two successive coats with no flash periodbetween coats. The basecoated panels were flash-heated for 5 minutes at200° F. prior to application of the clearcoats. Basecoat dry filmthickness was 0.4 mils (10 micrometers). The coating composition ofExample 24A above and a commercial two-component clearcoat (TKU-1050available from PPG Industries, Inc.) were spray applied to thebasecoated panels in two coats with a 60-second flash between coats,followed by a 10-minute ambient flash before curing for 30 minutes at285° F. (140.6° C.). Clearcoat dry film thickness was 1.6 mils for eachexample (40 micrometers).

[0404] The test panels prepared as described above were tested by MTSCorporation of Oak Ridge, Tenn. for surface penetration (or scratchdepth) as a function of load applied at a given rate over a givendistance. The Nano Indenter XP system was employed using a cube cornerindenter, at a scratch velocity of 20 μm/s, using normal load ramp of1000 μN/s to a maximum load of 25 mN over a scratch length of 500 μm.

[0405]FIG. 5 is a graph (scratch depth versus scratch distance) ofcoating surface penetration relative to load for the commercialtwo-component polyurethane coating (comparative example) usingnano-indenter techniques described above. Critical load determined forthis composition is 5.62 mN. As used herein, the term “critical load” isdefined from the onset of catastrophic cracking, i.e., failure of thecoating.

[0406]FIG. 6 is a graph (scratch depth versus scratch distance) ofcoating surface penetration relative to load for the two-componentcoating of Example 24A of the present invention described above usingthe nano-indenter techniques described above. Critical load determinedfor the composition of the invention is 11.74. The coating compositionof the present invention required a greater force to bring coatingfailure than did the commercial control under the same test conditions.

EXAMPLE 25

[0407] This example describes the preparation of a series of coatingcompositions of the present invention (Examples 25B-25G) which containincreasing amounts of particles in the form of colloidal silica.Comparative example 25A describes a coating composition which containsno particles. The test results in the following Table 5 illustrate theeffect of silica loading on post-weathering scratch resistanceproperties of the cured coating compositions.

Coating Composition Without Inorganic Particles

[0408] A coating composition was prepared by mixing under mild agitationthe following components: 35.9 weight percent of the acrylic polyol ofExample 23C; 29.1 weight percent DESMODUR N-3300; 20 weight percent ofthe siloxane polyol of Example A (this amount includes the siloxanepolyol incorporated in the form of the silica dispersion); 15 weightpercent CYMEL 202; 3 weight percent TINUVIN 98, 0.3 weight percentpolybutylacrylate flow additive, and 0.5 weight percent of the catalystof Example 12, where weight percentages were based on weight of totalresin solids of the components which form the coating composition.Particles were incorporated at levels ranging from 0 to 8.5 weightpercent into the composition described immediately above in the form ofthe colloidal silica dispersion of Example 19.

[0409] The compositions of Examples 25A-25G were applied to test panelsas described above for Example 24. The coated panels were subsequentlytested for initial and post-weathering scratch resistance properties asdescribed above. Test results are reported below in the following Table5. TABLE 5 Scratch Resistance After Initial Scratch Resistance 148 HoursQUV Exposure 20° Gloss 20° Gloss Example % Initial Initial 25 Silica**Retained % Gloss Retained % Gloss A* 0 88 79% 89 51% B 0.25 88 89% 8690% C 0.5 86 95% 88 91% D 1.0 86 95% 87 93% E 2.0 85 93% 86 95% F 4.0 8591% 86 95% G 8.5 86 88% 87 95%

[0410] The test data reported above in Table 5 illustrate thesignificant improvement in post-weathering scratch resistance attainedby incorporating even low levels (e.g. 0.25%) of silica in the coatingcompositions of the invention. Further, the data illustrates thatinitial and post-weathering scratch resistance results obtained usingcoating compositions having low levels of silica (i.e., 2.0% or less)are similar to those results obtained using coating compositions havinghigher levels of silica.

[0411]FIGS. 7 and 8 are electron micrographs of a transmission electronmicroscopy image (105,000× magnification) of a cross-section of thecoating composition according to Example 25E, and FIGS. 9 and 10 areelectron micrographs of a transmission electron microscopy image(105,000× magnification) of a cross-section of the coating compositionaccording to Example 25G.

EXAMPLE 26

[0412] This example describes the preparation of several coatingcompositions of the present invention (Examples 26B-26D) which are insolid particulate form. The compositions of Examples 26C and 26D containinorganic particles in the form of aluminum oxide. In the composition ofExample 26C, the aluminum oxide particles have been dispersed in asurface active agent and in the composition of Example 26D, the aluminumoxide particles have been dispersed in the polysiloxane polyol ofExample A. The compositions of Comparative Examples 26A and 26B eachcontain a surface active agent but no aluminum oxide. Each of thecompositions was prepared by blending the components listed below in aHenschel Blender for 60 to 90 seconds and subsequently extruding themixtures through a Wemer & Pfeider co-rotating twin screw extruder at ascrew speed of 450 rpm and an extrudate temperature of 100° C. to 125°C. (212° F. to 257° F.). Each of the extruded compositions was thenground to a particle size of 14 to 27 microns using an ACM Grinder (AirClassifying Mill from Micron Powder Systems of Summit, New Jersey toform a powder coating composition. Each powder coating composition waselectrostatically spray applied to test panels and evaluated for scratchresistance properties (as described below). Amounts listed belowrepresent parts by weight. Example Example Example Example Ingredients26A 26B 26C 26D Epoxy functional 69.05 69.05 68.98 49.11 acylic¹Dodecanedioic 22.68 22.68 22.65 22.04 acid Benzoin 0.20 0.20 0.20 0.20WAX C 0.60 0.60 0.60 0.60 MICROPOWDER² TINUVIN 144³ 2.00 2.00 2.00 2.00CGL-1545⁴ 2.00 2.00 2.00 2.00 HCA-1⁵ 2.00 2.00 2.00 2.00 ARMEEN M2C⁶0.37 0.37 0.37 0.37 Surface active — 1.10 — — agent A⁷ Surface active1.10 — — — agent B⁸ Aluminum oxide — — 1.20 — dispersion A⁹ Aluminumoxide — — — 20.58 dispersion B¹⁰ Total 100.00 100.00 100.00 100.00 #Publication WO 97/29854 and PCT patent application Ser. No. US97/16800,having a number average # molecular weight (“Mn”) range of 1000 to 5500;a range f glass transition temperature (Tg) # of 30° C. to 60° C. asmeasured or 50° C. to 85° C. as calculated by the # Acrylic GlassTransition Temperature Analyzer from Rohm and Haas Company, based on theFox equation; # and a range of epoxy content ranging from 35 to 85weight percent of the monomers to prepare the # epoxy acrylic polymer. #bis(methyl-2,2,6,6,-tetramethyl-4-piperidinyl)]dipropionate, anultraviolet light stabilizer # available from Ciba-Geigy Corp. #6-bis(2,4-dimethylphenyl)-1,3,5-triazine, an ultraviolet lightstabilizer available from Ciba-Geigy Corp. # hexyl acrytate, 23.5% ethylacrylate and 3% methacrylic acid. Polymerization was carried out atreflux # temperature in the presence of di-t-amyl peroxide and t-butylperacetate. The surface active agent was # then vacuum stripped to 100%resin solids. # 2-ethyl hexyl acrylate, 11.8% hydroxyl ethyl acrylateand 7% N,N-dimethylaminoethyl methacrylate. # Polymerization was carriedout at reflux temperature in the presence of VAZO 67 #(2,2=-Azobis-(2-methylbutyronitrile)). The surface active agent was thenvacuum stripped to 100% # resin solids. # 10% in the surface activeagent A described above. # then blended in the glycidyl methacrylatefunctional acrylic described above (87.5% acrylic/2.43% aluminum #oxide/10.07 siloxane polyol).

[0413] The powder coating compositions of Examples 26A-26D wereelectrostatically spray applied to test panels which were previouslycoated with an electrodepositable primer (commercially available asED5051 from PPG Industries, Inc. of Pittsburgh, Pa.). The powder coatingcompositions were applied at film-thickness of 2.3 to 2.8 mils (58 to 71micrometers) and cured for a period of 30 minutes at a temperature of293° F. (145° C.). The resulting coated panels were evaluated forinitial 20° gloss as described above. The coated panels were then testedfor scratch (mar) resistance properties using an Atlas Mar Tester andthe following procedure. Using a felt cloth clamped to the acrylicfinger on the arm of the instrument, a set of ten double rubs was run oneach coated panel to which BON AMI cleanser had been applied. Each ofthe tested panels was washed with cool tap water and thoroughly dried.The marred surface of each tested panel was then re-evaluated for 20°gloss. Scratch (mar) resistance test results are expressed as thepercentage of the 20° gloss retained after the surface is marred. Thatis, Scratch (mar) Resistance=(Marred 20° gloss/Initial 20° gloss)×100.The test data presented below in the following Table 6 is reported incomparative form, i.e., the results for Examples 26B to 26D are comparedwith test results for the control composition of Example 26A. A “+”indicates an improvement in scratch (mar) resistance properties over thecontrol composition. TABLE 6 Scratch (mar) Resistance Rating ComparativeExample A Control Example B + Example C ++ Example D 0

[0414] The mar resistance testing data presented in Table 6 illustratethe improvement in scratch (mar) resistance provided by the inclusion inpowder coating compositions of particles in the form of aluminum oxideparticles.

EXAMPLE 27

[0415] A coating composition of the present invention was prepared froma mixture of the following ingredients: Resin Total Weight IngredientsSolids (%) (Grams Methyl Amyl Ketone — 45.0 Tinuvin 928 3.0 3.0 Silicadispersion of 4.67 8.8 Example 23C Polysiloxane polyol of 10.33 10.33Example A Cymel 202 15.0 18.75 Acrylic polyol of 43.10 69.68 Example 23CTinuvin 292 0.5 0.5 Catalyst of Example 12 0.5 0.67 DESMODUR N3300 23.423.4 DESMODUR Z4470 3.5 5.0

[0416] A basecoat, Azuritblau, available from PPG (B&K) Germany wasapplied to primed steel automotive substrate. The basecoat was built toa film thickness ranging from between 12 and 15 microns, followed by afive minute heated flash at 80° C. before application of the coatingcomposition of Example 27. The coating composition of Example 27 wasspray-applied wet-on-wet to the basecoat to build a film thickness ofthe clearcoat ranging from between 35 and 45 microns. The coating wasthen cured 30 minutes at 130° C.

EXAMPLE 28

[0417] Silylated compounds for use in the coating compositions disclosedbelow were prepared as follows:

Silylated Compound A

[0418] This example illustrates the preparation of a silylated compoundthat is a half-acid ester of methyl hexahydrophthalic anhydride andtrimethylolpropane with residual carboxyl groups reacted with propyleneoxide.

[0419] A reaction vessel equipped with stirrer, thermocouple,temperature control, pumps and fitted with valved ports was charged with1202.9 grams trimethylolpropane (commercially available from Bayer USA),14.4 grams of triphenyl phosphine (commercially available from Aldrich),12.1 grams of triisooctyl phosphite (commercially available from GESpecialty Chemicals), and 800.0 grams of n-butyl acetate (commerciallyavailable from Union Carbide Chemicals and Plastics Co., Inc.).

[0420] The reactor was heated to 115° C. and 4436.7 grams ofmethylhexahydrophthalic anhydride (commercially available from MillikenChemical) were added over 90 minutes, and then held 4 hours at 115° C.1533.4 grams of propylene oxide (commercially available from FisherScientific Company) was charged to the reactor over 1 hour. The reactionwas held 4 hours until the acid value was less 5.38 mg KOH/gram.Residual propylene oxide was removed by vacuum distilling at 60 to 80 mmHg at 96° C. max. The resultant product had a total solids content of95.25%.

[0421] This product was silylated by the following procedure: 637.6grams (95.25% solids) of the previously described material were chargedto a reaction flask equipped with an overhead stirrer, nitrogen inlet,thermocouple, addition funnel, and condenser. The temperature wasincreased to 110° C. for one hour with nitrogen sparge to ensure thatthe system was dry. The temperature was then decreased to 85° C. undernitrogen blanket, at which time 180.9 grams hexamethyldisilazane(commercially available from Aldrich®) were added drop-wise over a 30minute period. The reaction was allowed to continue one additional hour,at which time a nitrogen sparge was introduced. The reaction wasconsidered complete when the size of the IR peak corresponding to thehydroxyl moiety was negligible. The solution was allowed to continuestirring under nitrogen sparge at 85° C. until the ammonia (by-product)was removed. Theoretical resin solids content was 96.3%.

Silylated Compound B

[0422] This example illustrates the preparation of a silylated compoundthat is a half-acid ester of methyl hexahydrophthalic anhydride andtrimethylolpropane with residual carboxyl groups reacted with propyleneoxide.

[0423] A reaction vessel equipped with stirrer, thermocouple,temperature control, pumps and fitted with valved ports was charged with550.0 grams trimethylolpropane (commercially available from Bayer USA),6.8 grams of triphenyl phosphine (commercially available from Aldrich®),5.57 grams of triisooctyl phosphite (commercially available from GESpecialty Chemicals), and 205.7 grams of n-butyl acetate (commerciallyavailable from Union Carbide Chemicals and Plastics Co., Inc.). Thereaction was heated to 115° C. 2030 grams of methylhexylhydrophthalicanhydride (commercially available from Milliken Chemical) was added over90 minutes. The reaction was held 4 hours at 115° C. The reactor wascooled to 100° C. and 769.9 grams of propylene oxide (commerciallyavailable from Fisher Scientific Company) was added over 1 hour. Thereaction was held 5 hours at 100C until the acid value was 3.1 mgKOH/gram. Residual propylene oxide was removed by vacuum distilling at60 to 80 mm Hg at 70C. The resultant product had a total solids contentof 95.08%.

[0424] This product was silylated by the following procedure: 3449.3grams (80.0% solids) of the previously described material were chargedto a reaction flask equipped with an overhead stirrer, nitrogen inlet,thermocouple, addition funnel, and condenser. The temperature wasincreased to 110° C. for one hour with nitrogen sparge to ensure thatthe system was dry. The temperature was then decreased to 85° C. undernitrogen blanket, at which time 821.9 grams hexamethyldisilazane(commercially available from Aldrich®) were added drop-wise over a onehour period. The reaction was allowed to continue 15 additional hours,at which time a nitrogen sparge was introduced. The reaction wasconsidered complete when the size of the IR peak corresponding to thehydroxyl moiety was negligible. The solution was allowed to continuestirring under nitrogen sparge at 85° C. until the ammonia (by-product)was removed. Theoretical resin solids content was 96.3%.

[0425] A silica dispersion, polysiloxane polyol and compositionpre-mixtures for use in the coating compositions disclosed below wereprepared as follows:

Silica Dispersion

[0426] The colloidal silica-dispersion was prepared from a proportionalyscaled batch of the silica dispersion of Example 23C.

Polysiloxane Polyol

[0427] The polysiloxane polyol was a product of the hydrosilylation of areactive silicone fluid with an approximate degree of polymerization of3 to 7, i.e., (Si—O)₃ to (Si—O)₇. The polysiloxane polyol was preparedfrom a proportionately scaled-up batch of the following mixture ofingredients in the ratios indicated: Equivalent Parts By WeightIngredients Weight Equivalents (kilograms) Charge I: Trimethylolpropane174.0 756.0 131.54 monoallyl ether Charge II: MASILWAX BASE¹ 156.7²594.8 93.21 Charge III: Chloroplatinic acid  10 ppm Toluene 0.23Isopropanol 0.07

[0428] To a suitable reaction vessel equipped with a means formaintaining a nitrogen blanket, Charge I and an amount of sodiumbicarbonate equivalent to 20 to 25 ppm of total monomer solids was addedat ambient conditions and the temperature was gradually increased to 75°C. under a nitrogen blanket. At that temperature, 5.0% of Charge II wasadded under agitation, followed by the addition of Charge III,equivalent to 10 ppm of active platinum based on total monomer solids.The reaction was then allowed to exotherm to 95° C. at which time theremainder of Charge II was added at a rate such that the temperature didnot exceed 95° C. After completion of this addition, the reactiontemperature was maintained at 95° C. and monitored by infraredspectroscopy for disappearance of the silicon hydride absorption band(Si—H, 2150 cm⁻¹).

Composition Pre-Mixtures

[0429] The following pre-mixtures of selected components of the coatingcompositions discussed below were prepared by sequentially mixing eachof the components with agitation. Pre-Mix 1: Parts by weight Ingredient(grams) Solid weights (grams) Methyl n-amyl ketone 18.0 — ButylCellosolve ® 18.0 — acetate¹ Butyl Carbitol ® 4.0 — acetate² TINUVIN384³ 1.58 1.50 TINUVIN 400⁴ 1.76 1.50 TINUVIN 292⁵ 0.40 0.40 SilicaDispersion 13.2 10.0 RESIMENE 757⁶ 27.1 26.3 LUWIPAL 018⁷ 11.9 8.7

[0430] Pre-Mix 2: Parts by weight Ingredient (grams) Solid weights(grams) Carbamoylated acrylic¹ 79.4 50.0 Carbamoylated polyester² 69.450.0 # in a solvent blend of (50% DOWANOL PM/50% propanoic acid,3-ethoxy ethyl ester) 75% Carbamoylated with # methyl carbamate. #hexahydrophthalic anhydride) 69% solids in a solvent blend of (44%DOWANOL PM/56% DOWANOL PM Acetate) 75% # carbamoylated with methylcarbamate.

[0431] Pre-Mix 3: Parts by weight Solid weights Ingredient (grams)(grams) Methyl n-amyl ketone 5.4 — Butyl Cellosolve ® 10.8 — acetate¹Butyl Carbitol ® 1.8 — acetate² TINUVIN ® 928³ 3.00 3.00 TINUVIN ® 292⁴0.40 0.40 TINUVIN ® 123⁵ 0.60 0.60 CYMEL ® 1130⁶ 29.9 29.9 RESIMENE ®741⁷ 11.3 9.9 # absorber available from Ciba Specialty Chemicals Corp. #Chemicals Corp. # stabilizer available from Ciba Specialty ChemicalsCorp.

[0432] Pre-Mix 4 Parts by Solid weight weights Ingredient (grams)(grams) Methyl n-amyl ketone 7.5 — Butyl Cellosolve ® acetate¹ 15.0 —Butyl Carbitol ® acetate² 2.50 — TINUVIN ® 928³ 3.00 3.00 TINUVIN ® 292⁴0.40 0.40 TINUVIN ® 123⁵ 0.60 0.60 Silica Dispersion 26.4 20.0Polysiloxane polyol 1.00 1.00 CYMEL ® 1130⁶ 29.9 29.9 RESIMENE ® 741⁷11.3 9.9

[0433] The pre-mixtures of ingredients from Pre-Mixes 1, 2, 3 and 4 wereused in Coating Compositions 5-16. The components for forming CoatingCompositions 5-16 are listed below in Tables 7-9. The amounts listed arethe total parts by weight in grams and the amount within parenthesis arepercentages by weight based on the weight of the resin solids of thecomponents which form the composition. Each component was mixedsequentially with agitation. TABLE 7 COATING COMPOSITION Ingredient 5 67 8 9 Pre-mix 1 95.9 (48.4) 95.9 (48.4) — — — Pre-mix 2 86.3 (58.0) 57.4(38.6) — — — Pre-mix 3 — — 63.2 (43.8) 63.2 (43.8) 63.2 (43.8) SilicaDispersion — — — 13.2 (10.0) 26.4 (20.0) Polysiloxane polyol — — — 8.0(8.0) 1.0 (1.0) Resin A — 20.1 (19.4) 62.5 (60.2) 46.9 (45.2) 46.9(45.2) Multiflow¹ — — 0.60 (0.30) — — Polybutyl acrylate² 0.50 (0.30)0.50 (0.30) 0.67 (0.40) 0.67 (0.40) 0.67 (0.40) Blocked acid catalyst³2.50 (1.00) 2.50 (1.00) — — — Acid catalyst⁴ — — 1.43 (1.00) 1.43 (1.00)1.43 (1.00) Reduction Information Methyl n-amyl ketone 3.49 — 3.60 2.892.10 Butyl Cellosolve ® 3.49 7.2 5.8 4.20 acetate⁵ Butyl Carbitol ®acetate⁶ 0.76 — 1.2 0.96 0.7 Spray viscosity⁷(sec) 28 28 37 38 38 Painttemperature (° F.) 73 73 72 72 72 230° F. (110° 52 58 64 66 68 C.)%Solids⁸ # number average molecular weight of 7934. # the aluminum dishto dissolve and/or disperse the coating. The coating is then heated inan oven for sixty minutes at 230° F. (110° C.). After removal from theoven, the aluminum dish is cooled, re-weighed, # and the non-volatilecontent (weight percent solids) is calculated using the followingequation: % Solids = (F − T) ÷ (I − T) * 100. Where: F = Final weight ofremaining coating and aluminum # dish in grams, I = Initial weight ofcoating and aluminum dish in grams, T = Tare weight of the aluminum dishin grams, and 100 is the conversion factor to percentage.

[0434] TABLE 8 COATING COMPOSITION Ingredient 10 11 12 13 Pre-mix 1 95.9(48.4) 95.9 (48.4) 95.9 (48.4) 95.9 (48.4) Pre-mix 2 86.3 (58.0) 57.4(38.6) 57.4 (38.6) 71.9 (48.3) Resin A — 20.1 (19.4) — — Resin B — —23.1 (19.4) 11.5 (9.7) Polybutyl acrylate¹ 0.50 (0.30) 0.50 (0.30) 0.50(0.30) 0.50 (0.30) Blocked acid catalyst² 2.50 (1.00) 2.50 (1.00) 2.50(1.00) 2.50 (1.00) Reduction Information Methyl n-amyl ketone 3.51 — —1.80 Butyl Cellosolve ® acetate³ 3.51 — — 1.80 Butyl Carbitol ® acetate⁴0.78 — — 0.40 Spray viscosity⁵ (sec) 28 29 28 28 Paint temperature (°F.) 73 73 74 74 230° F. (110° C.) % Solids⁶ 53 58 57 56

[0435] TABLE 9 COATING COMPOSITION Ingredient 14 15 16 Pre-mix 4 97.6(64.8) 97.6 (64.8) 97.6 (64.8) Pre-mix 2 — 33.6 (22.6) 16.8 (11.3) ResinB 53.8 (45.2) 26.9 (22.6) 40.4 (33.9) Polybutyl acrylate¹ 0.67 (0.40)0.67 (0.40) 0.67 (0.40) Acid catalyst² 1.43 (1.00) 1.43 (1.00) 1.43(1.00) Reduction Information Methyl n-amyl ketone 0.62 2.7 1.48 ButylCellosolve ® acetate³ 1.25 5.4 2.95 Butyl Carbitol ® acetate⁴ 0.21 0.900.49 Spray viscosity⁵ (sec) 27 28 28 Paint temperature (° F.) 74 74 74230° F. (110° C.) % Solids⁶ 66 63 63

Testing

[0436] Coating Compositions 5-16 were spray applied over a pigmentedbasecoat to form color-plus-clear composite coatings over primedelectrocoated steel panels. The panels used were cold rolled steelpanels (size 4 inches×12 inches (10.16 cm by 30.48 cm)) coated withED5100 electrocoat and PCV70100M primer, both available from PPGIndustries, Inc. The test panels are available as APR30471 from ACTLaboratories, Inc. of Hillsdale, Mich.

[0437] Coating Compositions 5-9 were tested over two differentbasecoats, namely: HWB9517, a black pigmented water-basedacrylic/melamine basecoat commercially available from PPG Industries,Inc, and a black pigmented water-based acrylic/melamine basecoat(Basecoat X), the formulation for which is given below. CoatingCompositions 10-16 were evaluated over Basecoat X. Basecoat X Parts bySolid weight weights Ingredient (grams) (grams) Hexyl Cellosolve ®¹ 20.0— 2-Butoxyethanol 20.0 — Phosphatized Epoxy² 1.00 0.60 TINUVIN 1130³3.00 3.00 CYMEL 1156⁴ 25.0 25.0 VISCOLAM 330⁵ 3.33 1.00 Deionized Water100.0 — Odorless Mineral Spirits⁶ 20.0 — BYK-032⁷ 3.90 2.00 AcrylicLatex⁸ 125.3 51.5 SETALUX 6802 AQ-24⁹ 61.2 15.0 Amine¹⁰ 3.00 — Blacktint paste¹¹ 47.6 11.5 ¹Ethylene glycol monohexyl ether solventcommercially available from Union Carbide Corp. ²Phosphatized epoxyprepared from EPON 828, a polyglycidyl ether of Bisphenol Aavailablefrom Shell Oil and Chemical Co.; reacted with phosphoric acid in an83:17 weight ratio. ³Substituted hydroxyphenyl benzotriazole availablefrom Ciba Specialty Chemicals Corp. ⁴Methylated melamine formaldehyderesin available from Cytec Industries, Inc. ⁵Acrylic thickener availablefrom Lamberti in Italy. ⁶Solvent available from Shell Chemical Co.⁷Defoamer available from Byk Chemie. ⁸The Acrylic Latex was prepared asfollows: The polyester was prepared in a four-neckround bottom flaskequipped with a thermometer, mechanical stirrer, condenser, dry nitrogensparge, and a heating mantle. The following ingredients were used:1103.0 g isostearic acid 800.0 g pentaerythritol 470.0 g crotonic acid688.0 g phthalic anhydride 6.1 g dibutyltin oxide 6.1 g triphenylphosphite 1170.0 g butyl acrylate 4.0 g lonol (butylated hydroxytoluene)The first six ingredients were stirred in the flask at 210° C. until 245ml ofdistillate was collected and the acid value dropped to 46. Thematerial was cooled to 77° C. and the last two ingredients were stirredin. The final product was a viscous yellow liquid with a hydroxyl valueof 54.0, a Gardner-Holdt viscosity of Z+, a weight average molecularweight of 45,600, and a non-volatile contentof 70.2%. A pre-emulsion wasprepared by stirring together the following ingredients: 286.0 gpolyester of example III 664.0 g butyl acrylate 30.0 g ethylene glycoldimethacrylate 20.0 g acrylic acid 46.4 g dodecylbenzenesulfonic acid(70% in isopropanol) 14.3 g dimethylethanolamine 1000.0 g water Thereaction was carried out using the same procedure and materials as inLatex Example I. The reaction exothermed from 23° C. to 80° C. The finalpH of the latex was 6.1, the nonvolatile content was 42.4%, the particlesize was 105 nm, and the Brookfield viscosity was 14 cps (spindle #1, 50rpm). ⁹Rheology control agent available from Akzo Nobel.¹⁰Dimethylethanolamine, 50% Aqueous, available from Union Carbide Corp.¹¹86B2792, 1300 MONARCH BLACK tint paste, available from PPG Industries.Inc. 1300 MONARCH BLACK is a black pigment available from Cabot Corp.,dispersed in an acrylic grind vehicle at a pigment to binder ratio (P/B)of 0.28.

[0438] Two coats of basecoat were automated spray applied to theelectrocoated and primed steel panels at ambient temperature (70° F.(21° C.)). No flash was permitted between the application of the twobasecoat layers. The total dry film thickness of the basecoat rangedfrom 0.5 to 0.7 mils (13 to 17 micrometers) was targeted. After thesecond basecoat application, a 1 to 10 minute air flash at ambienttemperature was given before force flashing the basecoated panels. Forpanels basecoated with HWB9517, the force flash was ten minutes at 200°F. (93° C.). The panels basecoated with Basecoat X were forced flashedfor five minutes at 200° F. (93° C.). Coating Compositions 5-16 wereeach automated spray applied to a basecoated panel at ambienttemperature in two coats with a ninety second ambient flash betweenapplications. Total clearcoat was applied at a 1.6 to 1.8 mils (41 to 46micrometers) dry film thickness. All coatings were allowed to air flashat ambient temperature for ten minutes. Panels prepared from eachcoating were baked for thirty minutes at 285° F. (141° C.) to fully curethe coating(s). The panels were baked in a horizontal position.

[0439] To test recoat adhesion, each panel was coated with another layerof basecoat and clearcoat or clearcoat only, as specified below.Examples 5-9 were recoated with HWB9517 or Basecoat X and CoatingCompositions 5-9, depending on the respective original panel. Examples10-16 were recoated with Basecoat X and Coating Compositions 10-16,depending on the respective original panel. For example, CoatingComposition 5 over HWB9517 original (prepared above) was recoated withHWB9517 and Coating Composition 5 clearcoat. Half of an original panelfrom Examples 5-16 was basecoated and clearcoated and the other half ofthe panel was clearcoated only. To recoat the panels, the bottom halvesof the original panels were covered with aluminum foil and then therespective basecoats were automated spray applied as described above.The foil was removed, resulting in an original panel with the upper halfcoated in basecoat and the bottom half still with only the originalcoating layers. The panels were force flashed as described above. Therespective clearcoat was then automated spray applied to the entirepanel as described above. The resulting panels were half coated inbasecoat/clearcoat from the original spray application and another layerof basecoat/clearcoat from the recoat spray application (B/C//B/C). Theother half of the resulting panel was coated in basecoat/clearcoat fromthe original spary application and another layer of clearcoat from therecoat spray application (B/C//C).

[0440] Properties for the coatings are reported below in Table 10 forExamples 5-9 over HWB9517 basecoat and Table 11 for Examples 5-16 overBasecoat X. TABLE 10 % 20° Gloss Retained after scratch testing² InitialPost weathering³ Knoop Recoat Adhesion⁵ Example # 20° Gloss¹ Initial 286Hours 618 Hours Hardness⁴ B/C//B/C B/C//C 5 85 79 82 84 10.3 0 0 6 85 1825 58 4.0 0 0 7 84 1 5 8 <2.0 0 4+ 8 84 6 14 20 <2.0 0 4 9 83 1 13 18<2.0 0 4

[0441] TABLE 11 % 20° Gloss Retained after scratch testing² Initial Postweathering³ Knoop Recoat Adhesion⁵ Example # 20° Gloss¹ Initial 286Hours 618 Hours Hardness⁴ B/C//B/C B/C//C 5 87 91 84 71 12.7 0 0 6 87 7880 64 9.9 4+ 0 7 87 27 20 20 13.8 5 4+ 8 88 81 28 26 11.5 4+ 4 9 88 7153 44 9.9 4+ 4 10 87 91 — — 10.9 1 0 11 86 67 — — 7.7 4+ 0 12 87 67 — —8.1 4+ 0 13 85 91 — — 10.4 4 0 14 87 49 — — 5.8 4+ 4+ 15 85 67 — — 6.7 41+ 16 87 59 — — 6.6 4+ 3+ # Electrical Devices Company of Chicago,Illinois. The abrasive paper used was 3M 281Q WETORDRY ™ PRODUCTION ™ 9micron polishing paper sheets, # which are commercially available from3M Company of St. Paul, Minnesota. Panels were then rinsed with tapwater and carefully patted dry with a paper towel. The 20° gloss wasmeasured (using the same gloss meter as that # used for the initial 20°gloss) on the scratched area of each lest panel. Using the lowest 20°gloss reading from the scratched area, the scratch # results arereported as the percent of the initial gloss retained after scratchtesting using the following # calculation: 100% * scratched gloss ÷initial gloss. Higher values for percent of gloss retained aredesirable. # UVA-340 bulbs in a QUV Accelerated Weathering Testeravailable through Q Panel Lab Products. Testing was as follows: a cycleof 70° C. for 8 hours exposure # to UVA followed by a condensation cycleat 50° C. for 4 hours with no UVA (total test time is reported in thetable). Using the lowest 20° gloss reading from the scratched area, thescratch results are reported as # the percent of the initial glossretained after post-weathering scratch testing using the followingcalculation: 100% * post-weathering scratched gloss ÷ # initial gloss.Higher values for percent of gloss retained are desirable. # coating byapplying a 25 gram load to the surface with a diamond tip. The size ofthe indentation is measured using a microscope. That indentation size isthen # converted to the Knoop Hardness measurement. The TukonMicrohardness Instrument used was the Tukon Microhardness Tester Model300 manufactured by Wilson Instruments, Division of Instron Corporation.# An eleven-blade claw with 1.5 mm spaced teeth (blade and handle/bladeholder are available from Paul N. Gardner Company, Inc.) was used toscribe the cured coating. # Two sets of scribes were made by scribingthe second set on top of and perpendicular to the first set. Detachedflakes and ribbons of coating were wiped off the panel and strappingtape (3M #898 available from 3M Company) # was smoothed firmly over thecrosshatch marking. Within 90 seconds of application, the tape wasremoved in one continuous motion directed toward the tester # and asparallel to the panel as possible. The scribed area was inspected andrated for removal of the recoat # layer to the substrate according tothe following scale: 5 = The edges of the cuts are completely smooth andnone of the lattice squares is detached. 4 = Small flakes of coating aredetached at intersections. Less than # five percent of the area isaffected. 3 = Small flakes of the coating are detached along edges andat intersections of cuts. The area affected is five # to fifteen percentof the lattice. 2 = The coating has flaked along the edges and on partsof the squares. The area affected is fifteen to thirty-five percent ofthe lattice. 1 = The coating has flaked along the edges of # cuts inlarge ribbons and whole squares have detached. The area affected isthirty-five to sixty-five percent of the lattice. 0 = Flaking anddetachment # worse than rating 1. Over sixty-five percent of the latticeis affected.

EXAMPLE 29

[0442] A dual cure (ultraviolet radiation and thermal cure) coatingcomposition was prepared and evaluated as discussed below.

[0443] The coating composition was made by adding each of theingredients under agitation in the order listed in the table below. Theacrylic polyol and isocyanurate were preblended before the addition tothe other ingredients. Ingredient Description Solids Weight SR355¹ DiTMPTetraacrylate 27.3 27.3 Clariant HIGHLINK Colloidal Silica 41.9 41.9 OG108-32 in tripropylene glycol diacrylate DAROCURE 4265³ Photoinitiator2.0 2.0 TINUVIN 400³ UV Absorber 3.0 3.0 TINUVIN 292³ Hindered AmineLight 0.8 0.8 Stabilizer RC-68-1497² Acrylic Polyol Resin 15.6 23.3DESMODUR N-3300⁴ Isocyanurate of HDI 9.4 9.4 Total 100.0 107.7 # 22.6%HPMA, 20.4% HEMA, 0.4% AA, and exhibiting the following # properties:solids 67% in AROMATIC 100 available from Exxon, Mw 2336, Mn 1236, OHvalue 116.8.

[0444] The coating composition was applied over pretreated andbasecoated panels as described below. The panels used were cold rolledsteel panels (size 4 inches×12 inches (10.16 cm by 30.48 cm)) coatedwith ED5000 electrocoat (available from PPG Industries, Inc). The testpanels are available from ACT Laboratories, Inc. of Hillsdale, Mich. Thebasecoat (BWB-8555 black waterborne basecoat available from PPGIndustries, Inc.) was spray applied at 0.6 mils (15 micrometers) dryfilm thickness and fully baked for 30 minutes at 285° F. (141° C.). Thecoating composition of the present invention was applied using a 7 mil(179 micrometers) drawdown bar over the basecoat to approximately1.0-1.2 mils (26-31 micrometers) dry film thickness. The clearcoat wasflashed at ambient temperature (25° C.) for five minutes and then curedusing ultraviolet light at 576 mJoules/cm² at a line speed of 70 feetper minute (21.3 meters per minute) and then thermally cured for 30minutes at 285° F. (141° C.).

[0445] The coating on the panel was evaluated for scratch resistance asfollows. 20° gloss was measured with a Statistical Novo-Gloss 20° glossmeter, available from Paul N. Gardner Company, Inc. Coated panels weresubjected to scratch testing by linearly scratching the coated surfacewith a weighted abrasive paper for ten double rubs using an Atlas AATCCScratch Tester, Model CM-5, available from Atlas Electrical DevicesCompany of Chicago, Ill. The abrasive paper used was 3M 281 Q WETORDRY™PRODUCTION™ 9 micron polishing paper sheets, which are commerciallyavailable from 3M Company of St. Paul, Minn. Panels were then rinsedwith tap water and carefully patted dry with a paper towel. The 20°gloss was measured (using the same gloss meter as that used for theinitial 20° gloss) on the scratched area of each test panel. Using thelowest 20° gloss reading from the scratched area, the scratch resultsare reported as the percent of the initial gloss retained after scratchtesting using the following calculation: 100%·scratched gloss÷initialgloss. Higher values for percent of gloss retained are desirable.

[0446] The test results are given in Table 12 below. TABLE 12 Initial20° 20° Gloss after Scratch % Gloss Clearcoat Gloss Testing RetentionUV/Thermal 82 79 96 Dual Cure

[0447] EXAMPLE 30

[0448] A polysiloxane polyol was prepared that was a product of thehydrosilylation of a reactive silicone fluid with an approximate degreeof polymerization of 3 to 7, i.e., (Si—O)₃ to (Si—O)₇. The polysiloxanepolyol was prepared from a proportionately scaled-up batch of thefollowing mixture of ingredients in the ratios indicated: EquivalentParts By Weight Ingredients Weight Equivalents (kilograms) Charge I:Trimethylolpropane 174.0 756.0 131.54 monoallyl ether Charge II:MASILWAX BASE¹ 156.7² 594.8 93.21 Charge III: Chloroplatinic acid 10 ppmToluene 0.23 Isopropanol 0.07

[0449] To a suitable reaction vessel equipped with a means formaintaining a nitrogen blanket, Charge I and an amount of sodiumbicarbonate equivalent to 20 to 25 ppm of total monomer solids was addedat ambient conditions and the temperature was gradually increased to 75°C. under a nitrogen blanket. At that temperature, 5.0% of Charge II wasadded under agitation, followed by the addition of Charge III,equivalent to 10 ppm of active platinum based on total monomer solids.The reaction was then allowed to exotherm to 95° C. at which time theremainder of Charge II was added at a rate such that the temperature didnot exceed 95° C. After completion of this addition, the reactiontemperature was maintained at 95° C. and monitored by infraredspectroscopy for disappearance of the silicon hydride absorption band(Si—H, 2150 cm⁻¹).

Silica Dispersion AA

[0450] A colloidal silica dispersion was prepared as follows. A 4-neckreaction flask equipped for vacuum distillation was flushed with N₂. Tothe reaction flask was added 1500.9 g of the polysiloxane polyoldescribed above, 3751.1 of ORGANOSILICASOL™ MT-ST colloidal silica whichis commercially available from Nissan Chemicals and 960.4 g of methylamyl ketone. The resulting mixture was vacuum distilled at 70 mm Hg and31° C.

Film Forming Compositions

[0451] Formulation pre-mixtures: (each component was mixed sequentiallywith agitation) Example 1 (99-346-91 A) Parts by Solid weight weightsIngredient (grams) (grams) Methyl n-amyl ketone 18.0 — ButylCellosolve ® acetate¹ 18.0 — Butyl Carbitol ® acetate² 4.0 — TINUVIN ®928³ 3.0 3.0 TINUVIN ® 292⁴ 0.40 0.40

[0452] The pre-mixture of ingredients from Example 1 was used inExamples 2 and 3. Compositions for Examples 2 and 3 are listed below inTable 1. The amounts listed are the total parts by weight in grams andthe amount within parenthesis are percentages by weight based on weightof resin solids. Each component was mixed sequentially with agitation.TABLE 13 Example 2 Example 3 Ingredient (99-346-93A) (99-346-93B)Example 1 Pre-mix 43.4 (3.4) 43.4 (3.4) Silica Dispersion AA 10.0 (7.0)10.0 (7.0) RESIMENE 757¹ 11.8 (11.4) 11.8 (11.4) Acrylic² 100.8 (65.5)74.9 (48.7) Polybutyl acrylate³ 0.50 (0.30) 0.50 (0.30) Blocked acidcatalyst⁴ 2.50 (1.00) 2.50 (1.00) CYLINK ® 2000⁵ 37.1 (19.1) — TRIXENEDP9B/1494⁶ — 51.3 (35.9) Reduction Information Methyl n-amyl ketone 2.39— Butyl Cellosolve ® acetate⁷ 2.39 — Butyl Carbitol ® acetate⁸ 0.53 —Spray viscosity⁹(sec) 29 26 Paint temperature (° F.) 73 74

Testing

[0453] The film forming compositions of Examples 2 and 3 were sprayapplied to a pigmented basecoat to form color-plus-clear compositecoatings over primed electrocoated steel panels. The panels used werecold rolled steel panels (size 4 inches×12 inches (10.16 cm by 30.48cm)) coated with ED5100 electrocoat and PCV70100M primer, both availablefrom PPG Industries, Inc. The test panels are available as APR30471 fromACT Laboratories, Inc. of Hillsdale, Mich.

[0454] A black pigmented water-based acrylic/melamine basecoat,available from PPG Industries, Inc. (Basecoat Z) was used. Theformulation for Basecoat Z is given below. Basecoat Z Parts by Solidweight weights Ingredient (grams) (grams) n-butoxypropanol, PNB¹ 45.0 —CYMEL 327² 38.9 35.0 TINUVIN 1130³ 3.20 3.20 Phosphotized Epoxy⁴ 0.800.50 Amine⁵ 2.00 — Acrylic Latex⁶ 109.4 46.5 Odorless Mineral Spirits⁷ 8— Polyurethane acrylic⁸ 42.6 10.0 Black tint paste⁹ 47.6 11.5 Amine⁵1.00 — DeIonized Water 67.7 — ¹Solvent available from LyondellPetrochemical. ²Methylated melamine formaldehyde resin available fromCytec Industries, Inc. ³Substituted hydroxyphenyl benzotriazoleavailable from Ciba Specialty Chemicals Corp. ⁴Phosphatized epoxyprepared from Epon 828, a polyglycidyl ether of Bisphenol A availablefrom Shell Oil and Chemical Co.; reacted with phosphoric acid in an83:17 weight ratio. ⁵Dimethylethanolamine, 50% aqueous, available fromUnion Carbide Corp. ⁶The Acrylic Latex was prepared as follows: Thepolyester was prepared in a four-neck round bottom flask equipped with athermometer, mechanical stirrer,condenser, dry nitrogen sparge, and aheating mantle. The following ingredients were used: 1103.0 g isostearicacid 800.0 g pentaerythritol 470.0 g crotonic acid 688.0 g phthalicanhydride 6.1 g dibutyltin oxide 6.1 g triphenyl phosphite 1170.0 gbutyl acrylate 4.0 g lonol (butylated hydroxytoluene) The first sixingredients were stirred in the flask at 210° C. until 245 ml ofdistillate was collected and the acid value dropped to 46. The materialwas cooled to 77° C. and the last two ingredients were stirred in. Thefinal product was a viscous yellow liquid with a hydroxyl value of 54.0,a Gardner-Holdt viscosity of Z+, a weight average molecular weight of45,600, and a non-volatile content of 70.2%. A pre-emulsion was preparedby stirring together the following ingredients: 286.0 g polyester ofexample III 664.0 g butyl acrylate 30.0 g ethylene glycol dimethacrylate20.0 g acrylic acid 46.4 g dodecylbenzenesulfonic acid (70% inisopropanol) 14.3 g dimethylethanolamine 1000.0 g water The reaction wascarried out using the same procedure and materials as in Latex ExampleI. The reaction exothermed from 23° C. to 80° C. The final pH of thelatex was 6.1, the nonvolatile content was 42.4%, the particle size was105 nm, and the Brookfield viscosity was 14 cps (spindle #1, 50 rpm).⁷Solvent available from Shell Chemical Co. ⁸Polyurethane acryliccomposed of 4% dimethylol propionic acid. 16% Desmodur W (available fromBayer), 9.3% dimeryl diisocyanate, 22.8% FORMREZ 66-56 (Witco Corp),5.7% MPEG 2000 (Union Carbide Corp.), 22.6% methyl methacrylate, 15.6%butyl acrylate, 1.6% ethyleneglycol dimethacrylate, 2.1% diethylenetriamine, 0.3% ammonium persulfate. ⁹Black pigment available from CabotCorp. as MONARCH BLACK 1300 dispersed in an acrylic grind vehicle (35%butyl acrylate, 30% styrene, 18% butyl methacrylate, 8.5% 2-hydroxyethylacrylate, 8.5% acrylic acid) at a total pigment to binder ratio (P/B) of0.35.

[0455] The basecoats was automated spray applied in two coats to theelectrocoated and primed steel panels at ambient temperature (70CF (21°C.)). No flash was given between the two basecoat applications. A totaldry film thickness of 0.66 mils (17 micrometers) was targeted. After thesecond basecoat application, a 1 to 10 minute air flash at ambienttemperature was given before force flashing the basecoated panels. Theforce flash was five minutes at 200° F. (93° C.). The clear coatingcompositions of Examples 2 and 3 were each automated spray applied tothe basecoated panel at ambient temperature in two coats with a ninetysecond ambient flash between applications. Total dry film thickness forthe clearcoats was 1.78 mils (45 micrometers). All coatings were allowedto air flash at ambient temperature for ten minutes. Panels preparedfrom each coating were baked for thirty minutes at 285° F. (141° C.) tofully cure the coating(s). The panels were baked in a horizontalposition.

[0456] Properties for the coatings are reported below in Table 14. TABLE14 %20° Gloss Retained after scratch testing² Initial Post weathering³Example # 20° Gloss¹ Initial 240 Hours 504 Hours 1028 Hours 2 92 92 8451 32 3 90 79 85 49 29 # paper sheets, which are commercially availablefrom 3M Company of St. Paul, Minnesota. Panels were then rinsed with tapwater and carefully patted dry with a paper towel. # The 20° gloss wasmeasured (using the same gloss meter as that used for the initial 20°gloss) on the scratched area of each test panel. Using the lowest 20°gloss reading from the scratched area, the scratch results are reportedas the percent of the initial gloss retained after scratch # testingusing the following calculation: 100% * scratched gloss ÷ initial gloss.Higher values for percent of gloss retained are desirable. # Testing wasas follows: a cycle of 70° C. for 8 hours exposure to UVA followed by acondensation cycle at 50° C. for 4 hours # with no UVA (total test timeis reported in the table). Using the lowest 20° gloss reading from thescratched area, the scratch results are reported as the percent of theinitial gloss retained after post-weathering scratch testing using thefollowing calculation: 100% * post-weathering scratched gloss ÷ initialgloss. # Higher values for percent of gloss retained are desirable.

EXAMPLE 31

[0457] A coating composition of the present invention was prepared froma mixture of the following ingredients: Resin Total Weight IngredientsSolids (%) (Grams Butyl Acetate — 11.1 DOWANOL PM Acetate — 28.6 ButylCellusolve Acetate — 4.1 Tinuvin 928 3.0 3.0 Silica dispersion ofExample 23C 6.7 8.8 Polysiloxane polyol of Example A 10.3 10.3 Cymel 20215.0 18.8 Acrylic polyol¹ 22.5 31.5 Setalux C-71761 VB-60² 20.4 34.9Tinuvin 292 0.5 0.5 Catalyst of Example 12 0.5 0.67 DESMODUR N3300 23.423.4 DESMODUR Z4470 3.5 5.0

[0458] A coating composition of the present invention was also preparedfrom a mixture of the following ingredients: Resin Total WeightIngredients Solids (%) (Grams Ethyl 3-ethoxypropionate — 38.7 Tinuvin928 3.0 3.0 Silica dispersion 6.7 8.8 of Example 23C Polysiloxane polyol10.3 10.3 of Example A Cymel 202 7.5 9.4 Acrylic polyol¹ 39.0 57.9Tinuvin 292 1.0 1.0 Catalyst of Example 12 0.5 0.7 DESMODUR N3300 16.616.6 DESMODUR Z4470 21.9 31.3

[0459] The compositions of the present invention can provide numerousadvantages in coating applications, including, but not limited to, goodinitial and retained mar resistance, good appearance properties such asgloss and distinctiveness of image, and physical properties such as goodflexibility and weatherability.

[0460] It will be appreciated by those skilled in the art that changescould be made to the embodiments described above without departing fromthe broad inventive concept thereof. It is understood, therefore, thatthis invention is not limited to the particular embodiments disclosed,but it is intended to cover modifications which are within the spiritand scope of the invention, as defined by the appended claims.

1-133. (Cancelled).
 134. A multi-component composite comprising (i) abasecoat deposited from a pigmented composition, and (ii) a compositionapplied over at least a portion of the basecoat, wherein the composition(ii) is formed from components comprising: (a) at least one polysiloxanecomprising at least one reactive functional group; (b) at least onereactant comprising at least one functional group that is reactive withat least one functional group selected from the at least one reactivefunctional group of the at least one polysiloxane and at least onefunctional group of the at least one reactant; and (c) a plurality ofparticles selected from inorganic particles, composite particles, andmixtures thereof;  wherein each component is different,  wherein the atleast one reactive functional group of the at least one polysiloxane issubstantially nonreactive with the particles,  wherein a retainedscratch resistance value of the composition (ii) when cured is greaterthan a retained scratch resistance value of a composition that does notcontain the plurality of particles wherein each component is different,and  wherein the composition (ii) when cured has an initial scratchresistance value such that after scratch testing greater than 40 percentof the initial 20° gloss is retained.
 135. A multi-component compositeaccording to claim 134, wherein each at least one reactive functionalgroup of the at least one polysiloxane, which may be identical ordifferent, is selected from a hydroxyl group, a carboxyl group, anisocyanate group, a blocked polyisocyanate group, a primary amine group,a secondary amine group, an amide group, a carbamate group, a ureagroup, a urethane group, a vinyl group, an unsaturated ester group, amaleimide group, a fumarate group, an anhydride group, a hydroxyalkylamide group, and an epoxy group.
 136. A multi-component compositeaccording to claim 134, wherein the at least one polysiloxane comprisesat least two reactive functional groups.
 137. A multi-componentcomposite according to claim 134, wherein each at least one reactivefunctional group of the at least one polysiloxane, which may beidentical or different, comprises at least one reactive functional groupselected from a hydroxyl group, a carbamate group, an epoxy group, acarboxyl group, and a carbamate group.
 138. A multi-component compositeaccording to claim 137, wherein each at least one reactive functionalgroup of the at least one polysiloxane, which may be identical ordifferent, comprises at least two reactive functional groups selectedfrom a hydroxyl group, and a carbamate group.
 139. A multi-componentcomposite according to claim 137, wherein each at least one reactivefunctional group of the at least one polysiloxane, which may beidentical or different, comprises an oxyalkylene group and at least twohydroxyl groups.
 140. A multi-component composite according to claim134, wherein the at least one polysiloxane, when added to the othercomponents of the composition, is present in the composition in anamount ranging from 0.01 to 90 weight percent based on total weight ofthe resin solids of the components which form the composition.
 141. Amulti-component composite according to claim 140, wherein the at leastone polysiloxane is present in an amount of at least 2 weight percent.142. A multi-component composite according to claim 141, wherein the atleast one polysiloxane is present in an amount of at least 5 weightpercent.
 143. A multi-component composite according to claim 142,wherein the at least one polysiloxane is present in an amount of atleast 10 weight percent.
 144. A multi-component composite according toclaim 134, wherein the particles are selected from fumed silica,amorphous silica, colloidal silica, alumina, colloidal alumina, titaniumoxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia,colloidal zirconia and mixtures of any of the foregoing.
 145. Amulti-component composite according to claim 134, wherein the particlesare surface treated.
 146. A multi-component composite according to claim134, wherein the particles include colloidal silica.
 147. Amulti-component composite according to claim 134, wherein the particleshave an average particle size less than 100 microns prior toincorporation into the composition.
 148. A multi-component compositeaccording to claim 134, wherein the particles have an average particlesize less than 50 microns prior to incorporation into the composition.149. A multi-component composite according to claim 134, wherein theparticles have an average particle size ranging from 1 to less than 1000nanometers prior to incorporation into the composition.
 150. Amulti-component composite according to claim 149, wherein the particleshave an average particle size ranging from 1 to 100 nanometers prior toincorporation into the composition.
 151. A multi-component compositeaccording to claim 150, wherein the particles have an average particlesize ranging from 5 to 50 nanometers prior to incorporation into thecomposition.
 152. A multi-component composite according to claim 134,wherein the particles, when added to the other components that form thecomposition, are present in the composition in an amount ranging from0.01 to 75 weight percent based on total weight of the resin solids ofthe components which form the composition.
 153. A multi-componentcomposite according to claim 152, wherein the particles are present inan amount of at least 0.1 weight percent.
 154. A multi-componentcomposite according to claim 152, wherein the particles are present inan amount of at least 0.5 weight percent.
 155. A multi-componentcomposite according to claim 152, wherein the particles are present inan amount of less than 20 weight percent.
 156. A multi-componentcomposite according to claim 152, wherein the particles are present inan amount of less than 10 weight percent.
 157. A multi-componentcomposite according to claim 134, wherein the at least one reactant isselected from at least one curing agent.
 158. A multi-componentcomposite according to claim 157, wherein the at least one curing agentis selected from an aminoplast resin, a polyisocyanate, a blockedpolyisocyanate, a polyepoxide, a polyacid, and a polyol.
 159. Amulti-component composite according to claim 157, wherein the at leastone curing agent is selected from an aminoplast resin, and apolyisocyanate.
 160. A multi-component composite according to claim 157,wherein the curing agent, when added to the other components that formthe composition, is present in an amount ranging from 1 weight percentto 65 weight percent based on total weight of the resin solids of thecomponents which form the composition.
 161. A multi-component compositeaccording to claim 160, wherein the curing agent is present in an amountof at least 5 weight percent.
 162. A multi-component composite accordingto claim 161, wherein the curing agent is present in an amount of atleast 10 weight percent.
 163. A multi-component composite according toclaim 134, wherein the components which form the composition comprise atleast one film-forming material different from (a).
 164. Amulti-component composite according to claim 163, wherein the at leastone film-forming material is selected from at least one additionalpolymer, in addition to and different from said at least onepolysiloxane, comprising at least one reactive functional group.
 165. Amulti-component composite according to claim 164, wherein the at leastone reactive functional group of the at least one polymer is selectedfrom a hydroxyl group, a carboxyl group, an isocyanate group, a blockedpolyisocyanate group, a primary amine group, a secondary amine group, anamide group, a carbamate group, a urea group, a urethane group, a vinylgroup, an unsaturated ester group, a maleimide group, a fumarate group,an anhydride group, a hydroxy alkylamide group, and an epoxy group. 166.A multi-component composite according to claim 165, wherein the at leastone reactive functional group of the at least one polymer is selectedfrom a hydroxyl group, and a carbamate group.
 167. A multi-componentcomposite according to claim 134, wherein the components which form thecomposition comprise at least one catalyst.
 168. A multi-componentcomposite according to claim 167, wherein the at least one catalyst ispresent in an amount sufficient to accelerate the reaction between theat least one functional group of the at least one reactant and the atleast one reactive functional group of the at least one polysiloxane.169. A multi-component composite according to claim 167, wherein the atleast one catalyst is an acid catalyst.
 170. A multi-component compositeaccording to claim 169, wherein the at least one catalyst is selectedfrom an acid phosphate, a substituted sulfonic acid and an unsubstitutedsulfonic acid.
 171. A multi-component composite according to claim 167,wherein the at least one catalyst is phenyl acid phosphate.
 172. Amulti-component composite according to claim 134, wherein the componentswhich form the composition comprise at least one surface active agent.173. A multi-component composite according to claim 172, wherein the atleast one surface active agent is selected from an anionic surfaceactive agent, a nonionic surface active agent and a cationic surfaceactive agent.
 174. A multi-component composite according to claim 134,wherein the at least one polysiloxane has the following structure (II)or (III):

wherein: m has a value of at least 1; m′ ranges from 0 to 75; n rangesfrom 0 to 75; n′ ranges from 0 to 75; each R, which may be identical ordifferent, is selected from H, OH, monovalent hydrocarbon groups,monovalent siloxane groups, and mixtures of any of the foregoing; andeach R^(a), which may be identical or different, comprises the followingstructure (IV): —R³—X  (IV) wherein each R³, which may be identical ordifferent, is selected from an alkylene group, an oxyalkylene group, analkylene aryl group, an alkenylene group, an oxyalkenylene group, and analkenylene aryl group; and each X, which may be identical or different,represents a group which comprises at least one reactive functionalgroup selected from a hydroxyl group, a carboxyl group, an isocyanategroup, a blocked polyisocyanate group, a primary amine group, asecondary amine group, an amide group, a carbamate group, a urea group,a urethane group, a vinyl group, an unsaturated ester group, a maleimidegroup, a fumarate group, an anhydride group, a hydroxy alkylamide group,and an epoxy group.
 175. A multi-component composite according to claim174, wherein (n+m) ranges from 2 to
 9. 176. A multi-component compositeaccording to claim 174, wherein (n′+m′) ranges from 2 to
 9. 177. Amulti-component composite according to claim 175, wherein (n+m) rangesfrom 2 to
 3. 178. A multi-component composite according to claim 176,wherein (n′+m′) ranges from 2 to
 3. 179. A multi-component compositeaccording to claim 174, wherein each X, which may be identical ordifferent, represents a group comprising at least one reactivefunctional group selected from a hydroxyl group and a carbamate group.180. A multi-component composite according to claim 174, wherein each X,which may be identical or different, represents a group comprising atleast two hydroxyl groups.
 181. A multi-component composite according toclaim 174, wherein X represents a group comprising at least onesubstituent selected from H, a monohydroxy-substituted group and a grouphaving the following structure (V): R⁴—(CH₂—OH)_(p)  wherein R⁴ is

when p is 2 and R³ is C₁ to C₄ alkyl, or R⁴ is

when p is 3, wherein a portion of X is a group having the structure (V).182. A multi-component composite according to claim 181, wherein m is 2and p is
 2. 183. A multi-component composite according to claim 134,wherein the polysiloxane (a) is the reaction product of at least thefollowing reactants: (i) at least one polysiloxane of the formula (VI):

wherein each substituent group R, which may be identical or different,represents a group selected from H, OH, a monovalent hydrocarbon group,a siloxane group, and mixtures of any of the foregoing; at least one ofthe groups represented by R is H, and n′ ranges from 0 to 100, such thatthe percent of Si—H content of the polysiloxane of formula (VI) rangesfrom 2 to 50; and (ii) at least one molecule which comprises at leastone functional group selected from a hydroxyl group, a carboxyl group,an isocyanate group, a blocked polyisocyanate group, a primary aminegroup, a secondary amine group, an amide group, a carbamate group, aurea group, a urethane group, a vinyl group, an unsaturated ester group,a maleimide group, a fumarate group, an anhydride group, a hydroxyalkylamide group, and an epoxy group and at least one unsaturated bondcapable of undergoing a hydrosilylation reaction.
 184. A multi-componentcomposite according to claim 183, wherein said at least one functionalgroup is selected from hydroxyl groups.
 185. A multi-component compositeaccording to claim 134, wherein the components from which thecomposition is formed comprise at least one material which has at leastone reactive functional group which is blocked with a silyl group. 186.A multi-component composite according to claim 185, wherein the silylblocking group has the following structure (IX):

wherein each R₁, R₂ and R₃, which may be identical or different, isselected from hydrogen, an alkyl group comprising from 1 to 18 carbonatoms, a phenyl group, and an allyl group.
 187. A multi-componentcomposite according to claim 185, wherein the at least one reactivefunctional group is selected from a hydroxyl group and a carboxyl group.188. A multi-component composite according to claim 185 comprising atleast one compound which can be reacted with the functional group toform the silyl group, wherein the at least one compound is selected fromhexamethyldisilazane, trimethylchlorosilane, trimethylsilyldiethylamine,t-butyl dimethylsilyl chloride, diphenyl methylsilyl chloride,hexamethyl disilylazide, hexamethyl disiloxane, trimethylsilyl triflate,hexamethyldisilyl acetamide and mixtures of any of the foregoing.
 189. Amulti-component composite according to claim 185, wherein the at leastone material comprises at least one linkage selected from an esterlinkage, an urethane linkage, a urea linkage, an amide linkage, asiloxane linkage and an ether linkage.
 190. A multi-component compositeaccording to claim 185, wherein the at least one material comprises areaction product having the following structure structure (X):


191. A multi-component composite according to claim 134, wherein the atleast one polysiloxane has at least one of the following structuralunits (I): R¹ _(n)R² _(m)SiO₍₄₋ n-m)/2  (I) wherein each R¹, which maybe identical or different, represents H, OH, or a monovalent hydrocarbongroup; each R², which may be identical or different, represents a groupcomprising at least one reactive functional group; wherein m and nfulfill the requirements of 0<n<4, 0<m<4 and 2≦(m+n)<4.
 192. Amulti-component composite according to claim 191, wherein each R²represents a group comprising at least one reactive functional groupselected from a hydroxyl group, a carboxyl group, an isocyanate group, ablocked polyisocyanate group, a primary amine group, a secondary aminegroup, an amide group, a carbamate group, a urea group, a urethanegroup, a vinyl group, an unsaturated ester group, a maleimide group, afumarate group, an anhydride group, a hydroxy alkylamide group, and anepoxy group.
 193. A multi-component composite according to claim 192,wherein R²represents a group comprising at least one reactive functionalgroup selected from a hydroxyl group, a carbamate group, a carboxylgroup, and an epoxy group.
 194. A multi-component composite according toclaim 134, wherein the particles are present in an amount of at least 5weight percent.
 195. A multi-component composite according to claim 134,wherein the composition (ii) when cured has an initial scratchresistance value such that after scratch testing greater than 50 percentof the initial 200 gloss is retained.
 196. A multi-component compositeaccording to claim 134, wherein the composition (ii) when cured has aretained scratch resistance value such that after scratch testinggreater than 30 percent of the initial 200 gloss is retained.
 197. Amulti-component composite according to claim 196, wherein thecomposition (ii) when cured has a retained scratch resistance value suchthat after scratch testing greater than 40 percent of the initial 200gloss is retained.
 198. A multi-component composite according to claim134, wherein the composition (ii) when cured has a concentration ofparticles within a surface region thereof which is greater than aconcentration of particles within a bulk region thereof.
 199. Amulti-component composite according to claim 134, wherein curedcomposition (ii) is a topcoat.
 200. A multi-component compositeaccording to claim 134, wherein cured composition (ii) is transparent.201. A method for making a multi-component composite comprising: (a)applying a pigmented composition to a substrate to form a basecoat (i);(b) applying a composition (ii) over at least a portion of the basecoat(i); and (c) curing the composition (ii) to form a cured composition;wherein the composition (ii) is formed from components comprising: (I)at least one polysiloxane comprising at least one reactive functionalgroup; (II) at least one reactant comprising at least one functionalgroup that is reactive with at least one functional group selected fromthe at least one reactive functional group of the at least onepolysiloxane and at least one functional group of the at least onereactant; and (III) a plurality of particles selected from inorganicparticles, composite particles, and mixtures thereof; wherein eachcomponent is different, wherein the at least one reactive functionalgroup of the at least one polysiloxane is substantially nonreactive withthe particles, wherein a retained scratch resistance value of thecomposition (ii) when cured is greater than a retained scratchresistance value of a composition that does not contain the plurality ofparticles wherein each component is different, and wherein thecomposition (ii) when cured has an initial scratch resistance value suchthat after scratch testing greater than 40 percent of the initial 20°gloss is retained.
 202. A method according to claim 201, wherein thecomposition (ii) is thermally cured after application to the substrate.203. A method according to claim 201, wherein the composition (ii) iscured by exposure to ionizing radiation after application to thesubstrate.
 204. A method according to claim 201, wherein the composition(ii) is cured by exposure to actinic radiation after application to thesubstrate.
 205. A method according to claim 201, wherein the composition(ii) is cured by exposure to (1) ionizing radiation or actinic radiationand (2) thermal energy after application to the substrate.